(R)-1-Phenylpropan-1-ol ((R)-1-Phenyl-1-propanol) [C9H12O] by Asch

Query Query

Results

Date

176 reactions in Reaxys

2018-07-03 17h:27m:58s (UTC)

OH H

1. Query

Search as: Product, As drawn, No mixtures ) AND (IDE.RN='1565-74-8') AND (IDE.INCHI='DYUQAZSOFZSPHD-SECBINFHSA-N') NOT (RX.RXRN=2041555))

1/258

2018-07-03 17:29:03

H (v2)

O OH

Rx-ID: 2681716 View in Reaxys 1/176 Yield 100 %

Conditions & References With P-1-(4',6'-dimethyl-2'-hydroxyphenyl)-2-(N,N-di-n-butylaminomethyl)naphthalene in hexane, Time= 16h, T= 20 °C Bringmann, Gerhard; Breuning, Matthias; Tetrahedron Asymmetry; vol. 9; nb. 4; (1998); p. 667 - 679 View in Reaxys

100 %

With titanium(IV) isopropylate, 1,3,5-[(M)-2-(2-HOCH2-1-naphthyl)-3,5-Me2C6H2OCH2]3-benzene in hexane, dichloromethane, Time= 16h, T= 40 °C Bringmann, Gerhard; Pfeifer, Robert-Michael; Rummey, Christian; Hartner, Kristina; Breuning, Matthias; Journal of Organic Chemistry; vol. 68; nb. 18; (2003); p. 6859 - 6863 View in Reaxys

100 %

With (1R,2R)-N,N'-bis[(2,4,6-trimethylphenyl)methylene]-1,2-cyclohexane-diamine, (R)-(+)-3,3'-diphenyl-[1,1'-binaphthalene]-2,2'-diol in hexane, dichloromethane, Time= 5h, T= -78 - -20 °C Mikami, Koichi; Angelaud, Remy; Ding, Kuiling; Ishii, Akihiro; Tanaka, Akito; Sawada, Naotaka; Kudo, Kenichi; Senda, Masaaki; Chemistry - A European Journal; vol. 7; nb. 3; (2001); p. 730 - 737 View in Reaxys

100 %

Stage 1: With (1S,2R,3S,5S)-6,6-dimethyl-2-morpholinobicyclo[3.1.1]heptan-3-ol, (1R,2S,3R,5R)-6,6-dimethyl-2-morpholinobicyclo[3.1.1]heptan-3-ol in hexane, Time= 18h, T= -15 - 0 °C , Inert atmosphere Stage 2: With water, ammonium chloride in hexane, T= 0 °C , optical yield given as percent ee, enantioselective reaction Binder, Caitlin M.; Bautista, April; Zaidlewicz, Marek; Krzeminski, Marek P.; Oliver, Allen; Singaram, Bakthan; Journal of Organic Chemistry; vol. 74; nb. 6; (2009); p. 2337 - 2343 View in Reaxys

99 %

With tricarbonyl(η6-arene)chromium(0) complex derived from (1R,2S)-N,N-dibutylnorephedrine in hexane, toluene, Time= 12h, T= 0 °C , other aldehydes, var. chiral tricarbonyl(η6-arene)chromium(0) complexes, Product distribution, Mechanism Jones; Heaton; Tetrahedron Asymmetry; vol. 4; nb. 2; (1993); p. 261 - 272 View in Reaxys

99 %

With tricarbonyl(η6-arene)chromium(0) complex derived from (1R,2S)-N,N-dibutylnorephedrine in hexane, toluene, Time= 12h, T= 0 °C Jones; Heaton; Tetrahedron Asymmetry; vol. 4; nb. 2; (1993); p. 261 - 272 View in Reaxys

99.5 %

With N,N-dibutyl-1,1-dibutylvalinol in hexane, toluene, Time= 48h, Ambient temperature Delair, P.; Einhorn, C.; Einhorn, J.; Luche, J. L.; Tetrahedron; vol. 51; nb. 1; (1995); p. 165 - 172 View in Reaxys

99 %

With titanium(IV) isopropylate, chiral binaphthol based ligand in dichloromethane, Time= 2h, T= -25 °C Kang, Seung-Wan; Ko, Dong-Hyun; Kim, Kyoung Hoon; Ha, Deok-Chan; Organic Letters; vol. 5; nb. 23; (2003); p. 4517 4519 View in Reaxys

99 %

With (1R,2S)-N,N-dibutylnorephedrine chromium tricarbonyl ethylzinc alkoxide in hexane, Time= 12h, T= 0 °C Heaton, Steven B.; Jones, Graham B.; Tetrahedron Letters; vol. 33; nb. 132; (1992); p. 1693 - 1696 View in Reaxys

99 %

Stage 1: With C19H23NO2S in hexane, benzene, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, benzene, Time= 12h, T= 0 - 20 °C , Inert atmosphere Stage 3: With hydrogenchloride in hexane, water, benzene, enantioselective reaction

2/258

2018-07-03 17:29:03

Lesniak, Stanislaw; Rachwalski, Michal; Sznajder, Ewelina; Kielbasinski, Piotr; Tetrahedron Asymmetry; vol. 20; nb. 20; (2009); p. 2311 - 2314 View in Reaxys 99 %

With titanium(IV) isopropylate, methyl 4,6-O-benzylidene-2-deoxy-2-trifluoromethylsulfonamido-η-D-glucopyranoside in dichloromethane, toluene, T= 0 - 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Bauer, Tomasz; Smolinski, Slawomir; Applied Catalysis A: General; vol. 375; nb. 2; (2010); p. 247 - 251 View in Reaxys

> 99 %

With 4-methyl-N-{[(1S,2S)-2-(pyrrolidin-1-yl)cyclohexyl]methyl}benzenesulfonamide in hexane, Time= 24h, T= 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Hirose, Takuji; Sugawara, Kazuyuki; Kodama, Koichi; Journal of Organic Chemistry; vol. 76; nb. 13; (2011); p. 5413 - 5428 View in Reaxys

99 %

With (1R,2R)-1-N-(butan-2-yl)-2-N-(diphenylphosphoryl)-cyclohexane-1,2-diamine in toluene, Time= 0.5h, Reagent/catalyst Huang, Huayin; Zong, Hua; Bian, Guangling; Song, Ling; Journal of Organic Chemistry; vol. 77; nb. 22; (2012); p. 10427 10434 View in Reaxys

99 %

Stage 1: With (diphenylphosphoryl)[(R)-[(2R,4S,5R)-5-ethenyl-1-azabicyclo[2.2.2]octan-2-yl](6-methoxyquinolin-4-yl)methyl]amine in toluene, Time= 0.5h, T= -30 °C , Inert atmosphere Stage 2: in toluene, Time= 6h, T= -30 - 20 °C , Inert atmosphere, Concentration, Reagent/catalyst, Solvent, Temperature, enantioselective reaction Shen, Bin; Huang, Huayin; Bian, Guangling; Zong, Hua; Song, Ling; Chirality; vol. 25; nb. 9; (2013); p. 561 - 566 View in Reaxys

99 %

4.22. Enantioselective addition of diethylzinc to benzaldehyde in presence of ligands 15-19, 29-35, 45 and 46 (General procedure) Enantioselective addition of diethylzinc to benzaldehyde in presence of ligands 15-19, 29-35, 45 and 46 (General procedure) To a solution of the corresponding ligand in 6 ml of hexane or toluene, Et2Zn (5.6 ml, 5.60 mmol of 1 M solution in hexane) was added dropwise at 0 °C. The mixture was stirred for 30 min at 0 °C and then benzaldehyde (0.288 ml, 2.83 mmol) was added at 0 °C. The reaction was stirred at room temperature and monitored by TLC (petroleum ether/Et2O = 5:1) until the full consumption of benzaldehyde. The mixture was quenched at 0 °C (aq. NH4Cl), extracted with Et2O (3 * 20 ml) and organic phase was dried over anhydrous Na2SO4. The solvent was evaporated in vacuo and the crude product was chromatographed (15 g silica gel, petroleum ether/Et2O = 6:1) to obtain pure 1-phenyl-1-propanol as a mixture of both enantiomers. For the ee determination of 1-phenyl-1-propanol, see Section 4.1 .

3/258

2018-07-03 17:29:03

Stage 1: With (1R,2R,4S,E)-3-(ferrocenylmethylidene)-2-(2-(dimethylamino)phenyl)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol in hexane, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, T= 0 - 20 °C , Inert atmosphere, enantioselective reaction Kamenova-Nacheva, Mariana; Dobrikov, Georgi M.; Dimitrov, Vladimir; Tetrahedron Asymmetry; vol. 27; nb. 17-18; (2016); p. 852 - 864 View in Reaxys 99 %

7 : 4.2.6.Typical procedure for the addition of diethylzinc to aldehydes using MeO-PEG-supported ferrocene 12 General procedure: Chiral ligand 12 (0.005mmol) was placed in a dried Schlenk tube under a nitrogen atmosphere. Freshly distilled toluene (2.0mL) was then added followed by diethylzinc (2.0mL, 1M in hexane). The resulting solution was cooled to 0°C and stirred for approximately 30min. The aldehyde (0.5mmol) was then added and the reaction mixture was stirred for 48h. The reaction was quenched with saturated ammonium chloride solution (4.0mL). The mixture was then extracted with diethyl ether, and the organic portion was washed with saturated aqueous NaCl. The combined organics were then dried over anhydrous MgSO4 and concentrated in vacuo. The crude compound was purified by flash chromatography to give the final product. 4.2.7 1Phenylpropan-1-ol 14a (0019) 99percent yield, 88percent ee, [η]D 20=+27.7 (c 2.2, CHCl3), [Determined by HPLC analysis Chiralcel OD-H column, Hexane/i-PrOH=100/2, Flow rate: 1mL/min, UV detection at 254nm, Retention time: tmajor=13.31min, tminor=17.24min];

NMR (400MHz, CDCl3) η 0.90 (t, 3H), 1.71–1.92 (m, 2H), 1.96 (br, 1H), 4.51–4.72 (m, 1H), 7.25–7.40 (m,

5H); 13C NMR (100MHz, CDCl3) η 144.8, 128.4, 127.4, 126.2, 75.9, 31.9, 10.2 Stage 1: With C39H43FeNO3Si in hexane, toluene, Time= 0.5h, T= 0 °C , Schlenk technique, Inert atmosphere Stage 2: in hexane, toluene, Time= 48h, T= 0 °C , Schlenk technique, Inert atmosphere, enantioselective reaction Zhao, Wen-Xian; Liu, Guan-Jun; Wang, Jingjing; Li, Feng; Liu, Lantao; Tetrahedron Asymmetry; vol. 27; nb. 22-23; (2016); p. 1133 - 1144 View in Reaxys 99 %

Enantioselective Addition of Diethylzinc to Aldehydes General procedure: The ligand 7 (0.10 mmol) was dissolved in anhyd toluene (1 mL) in a test tube. The solution was stirred for 5 min. A 1.0 M solution of Et2Zn in n-hexane (2.0 mmol, 2.0 mL) was then added, and after the mixture had been stirred for 5 min at the appropriate temperature, a solution of aldehyde (1.0 mmol) in anhyd toluene (1 mL) was added by syringe. The mixture was stirred for the time reported in Table 2. Sat. aq NH4Cl (10 mL) was added and the mixture was extracted with EtOAc (3 × 10 mL). The collected organic phases were combined, washed with H2O, dried (Na2SO4), and concentrated. GC or HPLC analysis was done after suitable dilution. General method for GC analysis: TInj: 260 °C, TDet: 260 °C (FID), H2: 1 mL/min, split 100:1. 1-Phenylpropan-1-ol. Yield: 0.134 g (99percent); colorless oil; [η]D20 +41.5 (c 1.0, CHCl3) {Lit.15[η]D20 +46.90 (c 1.0, CHCl3)}. Enantiomeric excess determined by GC using Chiralsil-Dex CB column[Oven 90 η 110 °C (1.5 °C/min)]. tR = 24.3 min (R); tR = 25.1 min(S). FTIR (neat): 3360, 2963, 1490, 1450, 1377, 1200, 974 cm–1. 1H NMR (300 MHz, CDCl3): η = 7.26–7.40 (m, 5 H, HAr), 4.59 (t, J = 6.6Hz, 1 H, CHOH), 1.69–1.91 (m, 2 H, CH2), 0.93 (t, J = 7.5 Hz, 3 H, CH3). 13C NMR (75 MHz, CDCl3): η = 144.7, 128.5, 127.6, 126.1, 75.9, 31.9,10.1. HRMS (ESI): m/z [M + Na]+ calcd for C9H12ONa: 159.0786; found:159.0780. Stage 1: With (1R,3S)-1-tert-butyl-6,7-dimethoxy-3-[(5R)-4-methoxy-6-methyl-5,6,7,8-tetrahydro[1,3]dioxolo[4,5-g]isoquinolin-5-yl]-1,3-dihydro-2-benzofuran-1-ol in hexane, toluene, Time= 0.0833333h, T= 20 °C Stage 2: in hexane, toluene, Time= 3h, T= 20 °C , Catalytic behavior, Reagent/catalyst, Temperature, enantioselective reaction Mohebbi, Maryam; Bararjanian, Morteza; Ebrahimi, Samad N.; Smieško, Martin; Salehi, Peyman; Synthesis (Germany); vol. 50; nb. 9; (2018); p. 1841 - 1848; Art.No: SS-2017-N0571-OP View in Reaxys

98 %

With butan-1-ol in hexane, toluene, Time= 5h, T= 20 °C Yun, Hongying; Wu, Yangjie; Wu, Yusheng; Ding, Kuiling; Zhou, Ying; Tetrahedron Letters; vol. 41; nb. 52; (2000); p. 10263 - 10266 View in Reaxys

98 %

Stage 1: With (Ra)-3,3'-bis(diphenylphosphinoyl)-BINOL in tetrahydrofuran, toluene, Time= 0.5h, T= -78 °C Stage 2: in tetrahydrofuran, toluene, Time= 12h, T= 0 °C Hatano, Manabu; Miyamoto, Takashi; Ishihara, Kazuaki; Advanced Synthesis and Catalysis; vol. 347; nb. 11-13; (2005); p. 1561 - 1568 View in Reaxys

98 %

With (R)-2,2'-dihydroxy-3,3'-di[(Me2N)2P(O)]-1,1'-binaphthyl in tetrahydrofuran, toluene, Time= 24h, T= 20 °C

4/258

2018-07-03 17:29:03

Hatano, Manabu; Miyamoto, Takashi; Ishihara, Kazuaki; Journal of Organic Chemistry; vol. 71; nb. 17; (2006); p. 6474 6484 View in Reaxys 98 %

With (R)-3,3'-bis[(Me2N)2P(=O)-]-BINOL in tetrahydrofuran, toluene, Time= 24h, T= 20 °C Hatano, Manabu; Miyamoto, Takashi; Ishihara, Kazuaki; Synlett; nb. 11; (2006); p. 1762 - 1764 View in Reaxys

98 %

With (+)-(1S,2S,4R)-1-methyl-4-(1-methylethylethyl)-2-(4-morpholinyl)-1-cyclohexanol in toluene, Time= 24h, T= 0 - 20 °C Patent; The Dow Chemical Company; Singaram, Bakthan; Chrisman, William; US6362373; (2002); (B1) English View in Reaxys

98 %

Stage 1: With N,N'-bis{[(1S,2R,4R)-7,7-dimethyl-2-hydroxynorborn-1-yl]carbonyl}homopiperazine in hexane, Time= 1h, T= 20 °C , Inert atmosphere Stage 2: With hydrogenchloride, water, optical yield given as percent ee, enantioselective reaction Sanchez-Carnerero, Esther M. Marquez; De Las Casas Engel, Tomas; Lora Maroto, Beatriz; De La Moya Cerero, Santiago; Chirality; vol. 23; nb. 7; (2011); p. 523 - 526 View in Reaxys

97 %

With titanium(IV) isopropylate, (Sa)-2,2'-bis[(S)-1-hydroxy-1H-perfluorooctyl]biphenyl in hexane, toluene, Time= 5h, T= -78 -30 °C Omote, Masaaki; Nishimura, Yuji; Sato, Kazuyuki; Ando, Akira; Kumadaki, Itsumaro; Tetrahedron; vol. 62; nb. 8; (2006); p. 1886 - 1894 View in Reaxys

97 %

With titanium(IV) isopropylate in dichloromethane, T= 0 °C Harada, Toshiro; Ukon, Takahiro; Tetrahedron Asymmetry; vol. 18; nb. 21; (2007); p. 2499 - 2502 View in Reaxys

97 %

4.3. Asymmetric addition of diethylzinc to aldehydes; generalprocedure General procedure: Chiral catalysts of type 4 (0.1 mmol) in dry toluene (5 mL) were placed in a round-bottomed flask. The mixture was cooled to 0 °C and a solution of diethylzinc (1.0 M sln. in hexane, 3.0 mmol) was added under argon. After stirring for 30 min, an aldehyde (1.0 mmol) was added at 0°C, and the mixture was stirred at room temperature overnight. Next, a 5percent HCl aqueous solution was added, the layers were separated, and the aqueous phase was extracted with diethyl ether (4×10 mL). The combined organic layers were washed with brine (10 mL) and dried over anhydrous MgSO4. The solvents were evaporated off to afford the crude alcohols 5a–e, which were purified via column chromatography on silica gel (hexane with ethyl acetate in gradient). The yields, specific rotations, enantiomeric excess values, and the absolute configurations of products 5a–e are collected in Table 3. The spectroscopic data were in full agreement with those reported in the literature. Stage 1: With C15H27NO in hexane, toluene, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, T= 0 - 20 °C , Inert atmosphere, Reagent/catalyst, enantioselective reaction Rachwalski, Michal; Tetrahedron Asymmetry; vol. 25; nb. 3; (2014); p. 219 - 223 View in Reaxys

96 %

With (R)-3,3-dimethyl-1-morpholinobutan-2-ol in hexane, Time= 24h, T= 0 °C Noyori, R.; Suga, S.; Kawai, K.; Okada, S.; Kitamura, M.; et al.; Journal of Organometallic Chemistry; vol. 382; nb. 1-2; (1990); p. 19 - 37 View in Reaxys

96 %

With 3-[(1'S,2'R)-2'-OH-1'-Me-2'-PhEt]-7-Me-3,7-diaza-C7H12N2 in hexane, toluene, Time= 24h, T= 0 °C , Addition Spieler, Jan; Huttenloch, Oliver; Waldmann, Herbert; European Journal of Organic Chemistry; nb. 3; (2000); p. 391 - 399 View in Reaxys

96 %

Stage 1: With (2S)-2-(benzyl(methyl)amino)-3-ethyl-1-phenylpentan-3-ol in hexane, T= 0 °C , Inert atmosphere Stage 2: in hexane, T= 0 - 20 °C , Inert atmosphere Stage 3: With water, ammonium chloride in hexane, optical yield given as percent ee, enantioselective reaction

5/258

2018-07-03 17:29:03

Zhang, Cong-Hai; Yan, Sheng-Jiao; Pan, Sheng-Qiang; Huang, Rong; Lin, Jun; Bulletin of the Korean Chemical Society; vol. 31; nb. 4; (2010); p. 869 - 873 View in Reaxys 95 %

With (1R,3S,4S)-2-<(R)-1-phenylethyl>-2-azabicyclo<2.2.1>heptane-3-exo-methanethiol in hexane, toluene, Time= 7h, Ambient temperature Nakano, Hiroto; Kumagai, Noriyuki; Matsuzaki, Hisao; Kabuto, Chizuko; Hongo, Hiroshi; Tetrahedron Asymmetry; vol. 8; nb. 9; (1997); p. 1391 - 1401 View in Reaxys

95 %

With (R)-1,1'-bis<3-<(2,5-dihexyloxy)phenyl>-2-naphthol> in toluene, Time= 4h, T= 0 °C Huang, Wei-Sheng; Hu, Qiao-Sheng; Pu, Lin; Journal of Organic Chemistry; vol. 63; nb. 5; (1998); p. 1364 - 1365 View in Reaxys

95 %

With titanium(IV) isopropylate, (S,S)-N,N'-bis(p-tolylsulfonyl)-trans-cyclohexane-1,2-diamine in hexane, toluene, Time= 15h, T= -30 °C Pritchett, Suzy; Woodmansee, David H.; Davis, Timothy J.; Walsh, Patrick J.; Tetrahedron Letters; vol. 39; nb. 33; (1998); p. 5941 - 5942 View in Reaxys

95 %

Stage 1: With (R)-3,3'-bis(2'',4''-dihexyloxyphenyl)-1,1'-binaphthol in toluene, Time= 0.25h, Substitution Stage 2: in toluene, Time= 4h, T= 0 °C , Addition Huang, Wei-Sheng; Hu, Qiao-Sheng; Pu, Lin; Journal of Organic Chemistry; vol. 64; nb. 21; (1999); p. 7940 - 7956 View in Reaxys

95 %

With (S,4Sp,13Rp)-C29H31NO2 in toluene, Time= 1.5h, T= 25 °C Wu, Xun-Wei; Zhang, Tang-Zhi; Yuan, Ke; Hou, Xue-Long; Tetrahedron Asymmetry; vol. 15; nb. 15; (2004); p. 2357 - 2365 View in Reaxys

95 %

With N-(2-hydroxybenzyl)-2-methylpropane-2-sulfinamide in hexane, toluene, Time= 18h, T= 20 °C Huang, Zhiyan; Lai, Hongshan; Qin, Yong; Journal of Organic Chemistry; vol. 72; nb. 4; (2007); p. 1373 - 1378 View in Reaxys

95 %

Stage 1: With (S,pR)-2-[2-(diferrocenylhydroxymethyl)ferrocenyl]-4-isopropyloxazoline in hexane, toluene, Time= 0.5h, T= 25 °C Stage 2: in hexane, toluene, T= 0 °C , Inert atmosphere Stage 3: With hydrogenchloride in hexane, water, toluene, optical yield given as percent ee Garabatos-Perera, Jose Ramon; Butenschoen, Holger; Journal of Organometallic Chemistry; vol. 694; nb. 13; (2009); p. 2047 - 2052 View in Reaxys

95 %

Stage 1: With (1S,2S,4R)-1,3,3-trimethyl-2-[(R)-2-(6-phenylpyridin-2-yl)phenyl]bicyclo-[2.2.1]heptan-2-ol in toluene, T= 0 20 °C , Inert atmosphere Stage 2: in toluene, Time= 96h, T= 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Leven, Matthias; Schloerer, Nils E.; Neudoerfl, Joerg M.; Goldfuss, Bernd; Chemistry - A European Journal; vol. 16; nb. 45; (2010); p. 13443 - 13449 View in Reaxys

95 %

4 :Reaction Example 1Asymmetric Diethylzinc Addition with Benzaldehyde Catalyzed by η-Amino Alcohols B and 5-7The application of 10 mol percent of η-amino alcohols B and 5-7 in the asymmetric addition of diethylzinc with benzaldehydes was initially tested at 0° C., and good yields along with excellent ee were obtained (Table 1). With (1S,2R)-7,7-dimethyl-1-pyrrolidin-1-yl-bicyclo[2.2.1]-heptan-2-ol in hexane, Time= 2h, T= 0 °C , Product distribution / selectivity Patent; UANG, Biing-Jiun; Wu, Chi-Rui; Wu, Hsyueh-Liang; US2011/313159; (2011); (A1) English View in Reaxys

6/258

2018-07-03 17:29:03

95 %

General procedure for enantioselective additions of diethylzinc to aldehydes General procedure: To a well-dried Schlenk tube charged with Bu4NBr (32.2 mg, 0.10 mmol, 10 mol percent), a solution of chiral ligand L1 (1 mL, 0.5 mol percent, 0.5 x 10-2 M in toluene) and dry toluene (1.0 mL) was added, then diethylzinc (1.0 M in hexane, 2.0 mL, 2.0 mmol, 2.0 equiv) was slowly added at 0 °C via a syringe under nitrogen atmosphere. After being stirred for 30 min, aldehyde (1a, 106 mg, 101.4 μL, 1.0 mmol) was added dropwise to the mixture at 0 °C . The mixture was stirred for 6 h at room temperature and quenched by addition of aqueous HCl (1.0 M, 5 mL). Extraction with EtOAc (10 mL x 3) gave combined organic layers that were washed with brine (10 mL), dried over MgSO4, and concentrated in vacuo to give a residue that was subjected to silica gel column chromatography (EtOAc/hexane = 1/10), which afforded the corresponding enantio-enriched secondary alcohol (2a) as a colorless oil. The ee value of the secondary alcohol was determined by Chiral GC. The absolute configuration of the alcohol was assigned as (R) by comparison of the optical rotation with reported data. Stage 1: With (1R,2R)-1-N-(diphenylphosphoryl)-2-N-(propan-2-yl)-cyclohexane-1,2-diamine, tetrabutylammomium bromide in hexane, toluene, Time= 0.5h, T= 0 °C , Inert atmosphere, Schlenk technique Stage 2: in hexane, toluene, Time= 6h, T= 0 - 20 °C , Inert atmosphere, Schlenk technique, Catalytic behavior, Reagent/catalyst, Time, enantioselective reaction Zong, Hua; Huang, Huayin; Bian, Guangling; Song, Ling; Tetrahedron Letters; vol. 54; nb. 21; (2013); p. 2722 - 2725 View in Reaxys

95 %

General procedure for the enantioselective addition of diethylzinc to aldehydes using 31 or 35 as the chiral ligand General procedure: Using 31 as the chiral ligand; To a solution of 31 (33.7mg, 0.05mmol) in hexane (0.75mL), diethylzinc (0.75mL of 1.0M solution in hexane, 0.75mmol) was slowly added at −15°C under a nitrogen atmosphere and stirred for 30min. Next, the aldehyde (0.5mmol) was added dropwise. The mixture was stirred for 2h at −15°C and then stirred for 4h at room temperature. The solution was then quenched with saturated aqueous HCl (10percent, 10mL). Extraction with EtOAc gave combined organic layers that were washed with brine, dried over Na2SO4, and concentrated in vacuo to give a residue, which was subjected to silica gel column chromatography, to afford the corresponding secondary alcohol (R)-37. Stage 1: With [(1R,2R)-2-[methyl(propan-2-yl)amino]-1,2-diphenylethyl]({[(1R,2R)-2-[methyl(propan-2-yl)amino]-1,2-diphenylethyl]amino}(phenyl)thiophosphoryl)amine in hexane, Time= 0.5h, T= -15 °C , Inert atmosphere Stage 2: in hexane, Time= 6h, T= -15 - 20 °C , Inert atmosphere, Solvent, Temperature, enantioselective reaction Yue, Huifeng; Huang, Huayin; Bian, Guangling; Zong, Hua; Li, Fangling; Song, Ling; Tetrahedron Asymmetry; vol. 25; nb. 2; (2014); p. 170 - 180 View in Reaxys

95 %

Asymmetric addition of diethylzinc to aldehydes: general procedure General procedure: The chiral catalyst (0.1mmol) in dry toluene (5mL) was placed in a round-bottom flask. The mixture was cooled to 0°C and a solution of diethylzinc (1.0M in hexane, 3.0mmol) was added under argon. After stirring for 30min, an aldehyde (1.0mmol) was added at 0°C, and the mixture was stirred at room temperature overnight. Next, 5percent HCl aqueous solution was added, the layers were separated and the aqueous phase was extracted with diethyl ether (4×10mL). The combined organic layers were washed with brine (10mL) and dried over anhydrous MgSO4. The solvents were evaporated to afford crude alcohols 14, which were purified via column chromatography on silica gel (hexane with ethyl acetate in gradient). The yields, specific rotations, enantiomeric excess values and the absolute configurations of products 14 are shown in Table 4. The spectroscopic data were in full agreement with those reported in the literature.13 Stage 1: With C29H27NO in hexane, toluene, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, T= 0 - 20 °C , Inert atmosphere, enantioselective reaction Jarzyski, Szymon; Lesniak, Stanislaw; Pieczonka, Adam M.; Rachwalski, Michal; Tetrahedron Asymmetry; vol. 26; nb. 1; (2015); p. 35 - 40 View in Reaxys

95 %

With (1S,4R)-(7,7-dimethyl-2-morpholin-4-yl-bicyclo[2.2.1]hept-1-yl)methanethiol in hexane, Time= 24h, enantioselective reaction Wu, Hsyueh-Liang; Wu, Ping-Yu; Cheng, Ying-Ni; Uang, Biing-Jiun; Tetrahedron; vol. 72; nb. 21; (2016); p. 2656 - 2665 View in Reaxys

94 %

With (R,R)-6,6'-bis-(1-hydroxy-2,2-dimethylpropyl)-2,2'-bipyridine in toluene, Time= 48h, T= -25 °C Bolm, Carsten; Zehnder, Margareta; Bur, Daniel; Angewandte Chemie; vol. 102; nb. 2; (1990); p. 206 - 208 View in Reaxys

7/258

2018-07-03 17:29:03

94 %

With (1R,2S)-(-)-1-phenyl-2-piperidinopropane-1-thiol in toluene, Time= 12h, T= 0 °C Kang, Jahyo; Lee, Jun Won; Kim, Joo In; Journal of the Chemical Society, Chemical Communications; nb. 17; (1994); p. 2009 - 2010 View in Reaxys

94 %

With chiral polybinaphthol in toluene, Time= 5h, T= 0 °C , Addition Hu, Qiao-Sheng; Huang, Wei-Sheng; Pu, Lin; Journal of Organic Chemistry; vol. 63; nb. 9; (1998); p. 2798 - 2799 View in Reaxys

94 %

With (R)-2-[7-(benzyloxypentyl)-3,7-diazabicyclo[3.3.1]non-3-yl]-1-phenylethanol in hexane, toluene, T= 0 - 20 °C , Product distribution, Further Variations: Reagents Lesma, Giordano; Danieli, Bruno; Passarella, Daniele; Sacchetti, Alessandro; Silvani, Alessandra; Tetrahedron Asymmetry; vol. 14; nb. 16; (2003); p. 2453 - 2458 View in Reaxys

94 %

Stage 1: With (2R,3S,3aS,4aR,6R,8aS)-2-isopropyl-6,9,9-trimethyl-3-phenyldecahydro-4aH-pyrrolo[2,1-b][1,3]benzoxazin-3ol in hexane, toluene, T= 20 °C , Inert atmosphere Stage 2: With ammonium chloride in hexane, water, toluene, optical yield given as percent ee, enantioselective reaction Andres, Celia; Infante, Rebeca; Nieto, Javier; Tetrahedron Asymmetry; vol. 21; nb. 18; (2010); p. 2230 - 2237 View in Reaxys

94 %

With (R)-3,3-dimethyl-1-piperidinobutan-2-ol in hexane, Time= 24h, T= -40 - 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Zacharia, Jamest.; Tanaka, Takanori; Uesaka, Yumiko; Hayashi, Masahiko; Synthesis (Germany); vol. 44; nb. 11; (2012); p. 1625 - 1627; Art.No: SS-2012-F0262-OP View in Reaxys

94 %

With (S)-2-anilinomethyl-1-benzylpyrrolidine in hexane, toluene, Time= 18.16h, Inert atmosphere, Solvent Hosoda, Naoya; Ito, Hiroki; Takimoto, Tatsuya; Asami, Masatoshi; Bulletin of the Chemical Society of Japan; vol. 85; nb. 9; (2012); p. 1014 - 1022 View in Reaxys

94 %

Asymmetric addition of diethylzinc to aldehydes: general procedure10 General procedure: Chiral catalysts of type 4 (0.1mmol) in dry toluene (5mL) were placed in a round-bottom flask. The mixture was cooled to 0°C and a solution of diethylzinc (1.0M in hexane, 3.0mmol) was added under argon. After stirring for 30min, the corresponding aldehyde (1.0mmol) was added at 0°C, and the mixture was stirred at room temperature overnight. Next, 5percent HCl aqueous solution was added, layers were separated and the aqueous phase was extracted with diethyl ether (4×10mL). The combined organic layers were washed with brine (10mL) and dried over anhydrous MgSO4. The solvents were evaporated to afford the crude alcohols 5a–e, which were purified via column chromatography on silica gel (hexane with ethyl acetate in gradient). The yields, specific rotations, enantiomeric excess values and the absolute configurations of products 5a–e are collected in Table 4. The spectroscopic data are in full agreement with those reported in the literature.10,12,20,21 Stage 1: With C13H19NO in hexane, toluene, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, T= 0 - 20 °C , Inert atmosphere, enantioselective reaction Pieczonka, Adam M.; Les̈niak, Stanisław; Jarzyński, Szymon; Rachwalski, Michał; Tetrahedron Asymmetry; vol. 26; nb. 2-3; (2015); p. 148 - 151 View in Reaxys

93 %

With titanium(IV) isopropylate, (+)-verbenone dimer-based bis(methanesulfonamide) in hexane, toluene, Time= 16h, T= -40 °C , Alkylation, addition Paquette, Leo A.; Zhou, Renjie; Journal of Organic Chemistry; vol. 64; nb. 21; (1999); p. 7929 - 7934 View in Reaxys

93 %

With (S)-1-(η-N,N-dimethylaminobenzyl)-2-naphthol in toluene, Time= 12h, T= 20 °C , Addition Cardellicchio, Cosimo; Ciccarella, Giuseppe; Naso, Francesco; Perna, Filippo; Tortorella, Paolo; Tetrahedron; vol. 55; nb. 51; (1999); p. 14685 - 14692

8/258

2018-07-03 17:29:03

View in Reaxys 93 %

With chiral cycloaminobenzyl-2-naphthol ligand in toluene, Time= 12h, T= 0 °C , Product distribution, Further Variations: Catalysts Lu, Jun; Xu, Xuenong; Wang, Cunde; He, Jiangang; Hu, Yuefei; Hu, Hongwen; Tetrahedron Letters; vol. 43; nb. 46; (2002); p. 8367 - 8369 View in Reaxys

93 %

With (1R,3S,4S,6S)-4-methyl-N-{4,7,7-trimethyl-4-(piperidin-1-yl)bicyclo[4.1.0]heptan-3-yl}-benzenesulfonamide in hexane, Time= 20h, T= 0 °C , Inert atmosphere Roszkowski, Piotr; Malecki, Pawel; Maurin, Jan K.; Czarnocki, Zbigniew; Synthesis (Germany); vol. 47; nb. 4; (2015); p. 569 - 574; Art.No: SS-2014-N0492-OP View in Reaxys

92.5 %

With (1R)-(CH2CMe3)-(3S)-[C(OH)Et2]-2-Me-tetrahydro-η-carboline in hexane, toluene, Time= 46h, T= 20 °C Zhu; Zhao; Zuo; Pittman Jr.; Dai; Hao; Tetrahedron Asymmetry; vol. 12; nb. 18; (2001); p. 2613 - 2619 View in Reaxys

92 %

Stage 1: With (1S,2R,4R)-7,7-dimethyl-1-morpholin-4-yl-bicyclo[2.2.1]heptan-2-ol in hexane, pentane, Time= 2h, T= 0 °C Stage 2: With ammonium chloride in hexane, water, pentane, optical yield given as percent ee, enantioselective reaction Wu, Zhi-Long; Wu, Hsyueh-Liang; Wu, Ping-Yu; Uang, Biing-Jiun; Tetrahedron Asymmetry; vol. 20; nb. 13; (2009); p. 1556 - 1560 View in Reaxys

92 %

Stage 1: With titanium(IV) isopropylate, (Sa)-2'-[(R)-hydroxy(phenyl)methyl]-(1,1'-binaphthalen)-2-ol in diethyl ether, hexane, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in diethyl ether, hexane, Time= 5h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Gao, Guang; Bai, Xing-Feng; Yang, Hua-Meng; Jiang, Jian-Xiong; Lai, Guo-Qiao; Xu, Li-Wen; European Journal of Organic Chemistry; nb. 26; (2011); p. 5039 - 5046 View in Reaxys

91 %

With (S)-6-methyl-3-(2-phenylethyl)-1-phenyl-4-piperidino-3-heptanol in hexane, Time= 12h, T= 0 °C , Addition Kawanami, Yasuhiro; Mitsuie, Tomoko; Miki, Misuzu; Sakamoto, Takanobu; Nishitani, Kazumi; Tetrahedron; vol. 56; nb. 2; (2000); p. 175 - 178 View in Reaxys

91 %

4.6. General procedure for the addition of ZnR2 to aldehydes General procedure: The Ni complex (0.1 equiv) was dissolved in anhydrous toluene(10 mL) in a Schlenk tube. The solution was stirred and cooled at0 C for 30 min, and then a solution of Et2Zn (1.1 M in toluene) orMe2Zn (1.0 M in toluene) (12 equiv) was added dropwise via a syringeunder N2 atmosphere. After stirring the mixture for 30 min atroom temperature, a solution of aldehyde (10 equiv) in dry toluenewas added dropwise via a syringe. The mixture was stirred at roomtemperature for 8 h, quenched with 1 M HCl aqueous (5 mL), andthe product was extracted into Et2O (310 mL). The combinedextracts were washed with KHCO3, dried with anhydrous MgSO4,and evaporated under vacuum. Purification by column chromatography(silica gel, 9:1 hexane/AcOEt as eluent) gave the pure alcoholas a colorless oil. All reactions were carried out using0.1e0.2 mL of aldehyde. The conversion and the selectivity of thereaction were determined by NMR spectroscopy, and the enantioselectivitywas determined by HPLC or GC on a chiral stationaryphase Stage 1: With C32H34N4NiO2 in toluene, Time= 0.5h, T= 0 - 20 °C , Inert atmosphere, Schlenk technique Stage 2: in toluene, Time= 12h, T= 20 °C , Schlenk technique, Inert atmosphere, enantioselective reaction Escorihuela, Jorge; Altava, Belen; Burguete, M. Isabel; Luis, Santiago V.; Tetrahedron; vol. 69; nb. 2; (2013); p. 551 - 558 View in Reaxys

90 %

With pyrrolidine in hexane, temp. 0 deg C to r.t.; other C2-symmetric pyrrolidines as catalyst; enantioselectivity, Product distribution Masaki; Oda; Kazuta; Usui; Itoh; Xu; Tetrahedron Letters; vol. 33; nb. 35; (1992); p. 5089 - 5092 View in Reaxys

9/258

2018-07-03 17:29:03

90 %

With (R)-N-trityl-aziridinyl(diphenyl)methanol in hexane, toluene, T= 20 °C , Addition Lawrence, Corrine F.; Nayak, Sandip K.; Thijs, Lambertus; Zwanenburg, Binne; Synlett; nb. 10; (1999); p. 1571 - 1572 View in Reaxys

90 %

With chiral cis-cyclopropane-based amino alcohol ligand in hexane, toluene, Time= 48h, T= -15 °C Zhong, Jiangchun; Guo, Hongchao; Wang, Mingan; Yin, Mingming; Wang, Min; Tetrahedron Asymmetry; vol. 18; nb. 6; (2007); p. 734 - 741 View in Reaxys

90 %

With 1(R)-C(Ph2)OH-2,2-Me2-3(S)-(morpholin-4-yl-CH2)-cyclopropane in hexane, Time= 48h, T= -15 °C Zhong, Jiangchun; Wang, Mingan; Guo, Hongchao; Yin, Mingming; Bian, QingHua; Wang, Min; Synlett; nb. 11; (2006); p. 1667 - 1670 View in Reaxys

90 %

Stage 1: With N-((1S,2R)-1-hydroxy-1-phenylpropan-2-yl)furan-2-carboxamide in hexane, toluene, T= 0 °C Stage 2: With hydrogenchloride, water in hexane, toluene, enantioselective reaction Ananthi, Nallamuthu; Balakrishnan, Umesh; Vinu, Ajayan; Ariga, Katsuhiko; Velmathi, Sivan; Tetrahedron Asymmetry; vol. 20; nb. 15; (2009); p. 1731 - 1735 View in Reaxys

90 %

4.5. Enantioselective addition of diethylzinc to aldehydes General procedure: A solution of diethylzinc (1 M in n-hexane, 1.1 mL) was added to a solution of a chiral catalyst (0.025 mmol, 8.2 mg, 5 mol percent) in dry toluene under a nitrogen atmosphere. The mixture was cooled to 0 °C and stirred for 30 min. A freshly distilled aldehyde (0.5 mmol) was added to the mixture. The resulting mixture was stirred for 10 h at 0-5 °C and then allowed to warm to room temperature, and stirred another 38 h at the same temperature. The reaction was quenched by the addition of saturated aqueous NH4Cl (4 mL). The mixture was extracted with Et2O (3 .x. 8 mL). The combined organic layers were washed with brine, dried over anhydrous Na2SO4, and evaporated under reduced pressure. Purification of the residue by preparative silica gel TLC plate afforded the corresponding products. The ee was determined by HPLC analyses using a chiral column. Stage 1: With diphenyl-((R)-1-((S)-1-phenylethyl)aziridin-2-yl)-methanol in hexane, toluene, Time= 48.5h, T= 0 - 25 °C , Inert atmosphere Stage 2: With ammonium chloride in hexane, water, toluene, Saturated solution, optical yield given as percent ee, enantioselective reaction Wang, Min-Can; Wang, Yong-Hui; Li, Gao-Wei; Sun, Ping-Ping; Tian, Jie-Xi; Lu, Hui-Jie; Tetrahedron Asymmetry; vol. 22; nb. 7; (2011); p. 761 - 768 View in Reaxys

89 %

With polystyrene-bound (R)-3,3'-bis(o-methoxyphenyl)-cyclo-BINOL in dichloromethane, Time= 7h, T= 0 °C Lipshutz; Shin; Tetrahedron Letters; vol. 41; nb. 49; (2000); p. 9515 - 9521 View in Reaxys

89 %

With 2-exo-morpholinoisobornane-10-thiol in hexane, Time= 28h, T= 0 °C , Inert atmosphere, Reagent/catalyst, Temperature, Time, enantioselective reaction Cheng, Ying-Ni; Wu, Hsyueh-Liang; Wu, Ping-Yu; Shen, Ying-Ying; Uang, Biing-Jiun; Chemistry - An Asian Journal; vol. 7; nb. 12; (2012); p. 2921 - 2924 View in Reaxys

88 %

With (S)-2-{N-[(2-hydroxy-3-tert-butylphenyl)-phenyl-methylene]amino}-3,3-dimethyl-1-butanol in hexane, Time= 24h, T= 0 °C Tanaka, Takanori; Yasuda, Yorinobu; Hayashi, Masahiko; Journal of Organic Chemistry; vol. 71; nb. 18; (2006); p. 7091 7093 View in Reaxys

88 %

Stage 1: With chiral (ferrocenyl)(2-aziridinyl)methanol-based catalyst in hexane, toluene, Time= 0.5h, T= 20 °C Stage 2: in hexane, toluene, Time= 10h, T= 20 °C , Further stages.

10/258

2018-07-03 17:29:03

Bulut, Adnan; Aslan, Ayhan; Izgue, Enver Cagri; Dogan, Oezdemir; Tetrahedron Asymmetry; vol. 18; nb. 8; (2007); p. 1013 - 1016 View in Reaxys 88 %

Stage 1: With (1'R,2S,3S)-1-(1'-phenylethyl)-2-phenyl-3-hydroxyazetidine in toluene, Time= 0.333333h, T= 20 °C Stage 2: in toluene, Time= 29h, T= 20 °C , Inert atmosphere, enantioselective reaction Zhang, Zhanbin; Li, Min; Zi, Guofu; Chirality; vol. 19; nb. 10; (2007); p. 802 - 808 View in Reaxys

87 %

With titanium(IV) isopropylate, chiral p-toluenesulfonylaminocyclohexyl-based ligand in hexane, toluene, Time= 6h, T= -30 °C Bisai, Alakesh; Singh, Pradeep K.; Singh, Vinod K.; Tetrahedron; vol. 63; nb. 3; (2007); p. 598 - 601 View in Reaxys

85%

7 : Example 7 - Representative diethylzinc addition reaction catalyzed by (lS,2R,47?)-(7,7- dimethyl-2-morpholinobicyclo[2.2.11heptan-l-yl)methanethiol, (-)-2-exo- morpholinoisoborne-10-thiol (MITH; (la)) prepared from (lS,2R,4R)-(7,7dimethyl-2- morpholinobicyclo[2.2.11heptan-l-yl)methanethiol hydrochloride (MITH»HC1; (lb)) Example 7 - Representative diethylzinc addition reaction catalyzed by (lS,2R,47?)-(7,7- dimethyl-2-morpholinobicyclo[2.2.11heptan-l-yl)methanethiol, (-)-2-exo- morpholinoisoborne-10-thiol (MITH; (la)) prepared from (lS,2R,4R)-(7,7-dimethyl-2- morpholinobicyclo[2.2.11heptan-l-yl)methanethiol hydrochloride (MITH»HC1; (lb))[0134] A solution of ( l ^R^^ -dimethyl^-morpholinobicycIoP^. l lheptan- l - yl)methanethiol hydrochloride (M ITH'HCl; (lb)) (58 mg, 0.20 mmol) in ^-heptane ( 1 0 mL) was extracted with I M Na2C03 ( 1 0 mL). After separation of layers, the /7-heptane layer was washed with 10percent aq. NaCl (5 mL) and concentrated. The residual oil was co-evaporated with ^-heptane ( 10 mL) to give M ITH free base as a colorless oil. To the oil was added diethylzinc (3.0 mmol, 1.0 M in hexanes) at ambient temperature, and the mixture was stirred for 1 0 minutes. Neat benzaldehyde (200 ??, 2.0 mmol) was added in one portion at 0 °C. Upon completeconsumption of benzaldehyde as judged by TLC, sat. aq. NH4CI (3 mL) was slowly added to the reaction product mixture followed by ethyl acetate (20 mL). The mixture was washed twice with I N aq. HCI (20 mL each) and brine (5 mL), dried over solid Na2S04 and concentrated to give a colorless oil which was purified by silica gel column chromatography ( 1 : 10 ethyl acetate/«- heptane) to give ( ?)- l phenyl-propanol as a colorless oil (232 mg; 85percent; 96.3percent e.e.). Stage 1: With (1S,4R)-(7,7-dimethyl-2-morpholin-4-yl-bicyclo[2.2.1]hept-1-yl)methanethiol in hexane, Time= 0.166667h, T= 20 °C Stage 2: in hexane, Time= 16h, T= 0 °C , Catalytic behavior, Reagent/catalyst, Time, stereoselective reaction Patent; SCINOPHARM TAIWAN, LTD.; HENSCHKE, Julian Paul; WU, Ping-Yu; WO2013/80049; (2013); (A2) English View in Reaxys

84.6 %

With (1S,2R)-N,N-dimethyl-2-hydroxy-1,2-diphenyl-ethylamine in hexane, toluene, Time= 48h, Ambient temperature Li; Jiang; Mi; Tetrahedron Asymmetry; vol. 3; nb. 11; (1992); p. 1467 - 1474 View in Reaxys

83 %

With chiral secondary amino alcohol catalyst in toluene, Ambient temperature Tanaka, Kazuhiko; Ushio, Hideki; Suzuki, Hitomi; Journal of the Chemical Society, Chemical Communications; nb. 22; (1989); p. 1700 - 1701 View in Reaxys

80 %

With (1S,2S,4R)-1-methyl-4-(1-methylethenyl)-2-(1-piperidinyl)cyclohexanol in toluene, Time= 24h, T= 0 - 20 °C Patent; The Dow Chemical Company; Singaram, Bakthan; Chrisman, William; US6362373; (2002); (B1) English View in Reaxys

80 %

With (1S,2S,4R)-2-(benzyl-methylamino)-1-methyl-4-(1-methylethenyl)cyclohexanol in toluene, Time= 24h, T= 0 - 20 °C Patent; The Dow Chemical Company; Singaram, Bakthan; Chrisman, William; US6362373; (2002); (B1) English View in Reaxys

80 %

With (1S,2S,4R)-1-methyl-4-(1-methylethenyl)-2-(1-pyrrolidinyl)cyclohexanol in toluene, Time= 24h, T= 0 - 20 °C Patent; The Dow Chemical Company; Singaram, Bakthan; Chrisman, William; US6362373; (2002); (B1) English View in Reaxys

79 %

Stage 1: With 1-butyl-3-[[[[(1S,2-exo,3-exo)-3-hydroxy-1,7,7-trimethylbicyclo-[2.2.1]hept-2-yl]methyl]amino]methyl]pyridinium bis(trifluoromethanesulfonyl)imide in hexane, dichloromethane, Time= 0.5h, T= 0 °C , Inert atmosphere

11/258

2018-07-03 17:29:03

Stage 2: in hexane, dichloromethane, Time= 48h, T= 20 °C , Inert atmosphere Stage 3: With hydrogenchloride in hexane, dichloromethane, water, Inert atmosphere, enantioselective reaction Vasiloiu, Maria; Leder, Sonja; Gaertner, Peter; Mereiter, Kurt; Bica, Katharina; Organic and Biomolecular Chemistry; vol. 11; nb. 46; (2013); p. 8092 - 8102 View in Reaxys 79 %

With 1-[(S)-4-isopropyl-5,5-dimethyloxazolinyl]-2-(Rp)-(diferrocenylmethanol)ferrocene in hexane, Time= 0.333333h, T= -20 °C , Schlenk technique, Inert atmosphere, Temperature, Solvent Nottingham, Chris; Benson, Robert; Müller-Bunz, Helge; Guiry, Patrick J.; Journal of Organic Chemistry; vol. 80; nb. 20; (2015); p. 10163 - 10176 View in Reaxys

78 %

With phenyl)hexan-3-ol in hexane, toluene, Time= 4h, T= 20 °C , Addition Malezieux, Bernard; Andres, Roman; Gruselle, Michel; Rager, Marie-Noelle; Thorimbert, Serge; Tetrahedron Asymmetry; vol. 10; nb. 17; (1999); p. 3253 - 3257 View in Reaxys

74 %

Stage 1: With (3R,5R)-1-benzyl-5-trityloxypiperidin-3-ol in toluene, Time= 0.5h, T= 0 °C Stage 2: in toluene, Time= 24h, T= 20 °C Roudeau, Remi; Gomez Pardo, Domingo; Cossy, Janine; Tetrahedron; vol. 62; nb. 10; (2006); p. 2388 - 2394 View in Reaxys

74 %

4.6.1. General procedure D General procedure: A mixture of 2s (0.0060 mmol) and diethylzinc (0.40 mL, 0.40 mmol; 1.05 M solution in hexane) in hexane (1.00 mL) was stirred at room temperature for 1 h. Then the mixture was cooled to appropriate temperature, added aldehyde 3 (0.200 mmol), and stirred for 24 h. The mixture was then quenched by NH4Cl aq and extracted with EtOAc three times. The combined organic layers were washed with brine and dried over Na2SO4. The crude product was purified by PTLC on silica gel (EtOAc/hexane = 1:4) to give 4. Stage 1: With N-[(1S)-1-(2,3-dimethoxyphenyl)ethyl]-4-methylbenzenesulfonamide in hexane, Time= 1h, T= 20 °C , Inert atmosphere Stage 2: in hexane, Time= 24h, T= 0 °C , Inert atmosphere Stage 3: With ammonium chloride in hexane, water, optical yield given as percent ee, enantioselective reaction Yoshida, Kazuhiro; Akashi, Naohisa; Yanagisawa, Akira; Tetrahedron Asymmetry; vol. 22; nb. 11; (2011); p. 1225 - 1230 View in Reaxys

73 %

With chiral octahydro-cyclopenta[b]pyrrole aminoalcohol catalyst in toluene, Time= 40h, T= 23 °C , Alkylation Wassmann, Suzanne; Wilken, Joerg; Martens, Juergen; Tetrahedron Asymmetry; vol. 10; nb. 22; (1999); p. 4437 - 4445 View in Reaxys

72 %

With CH3CH<N(CH3)(CH(CH3)2)>CH2OHC6H5OH in hexane, Time= 48h, T= 25 °C , enantiomer excess as a function of various catalyst Chaloner, Penny A.; Perera, Renuka S. A.; Tetrahedron Letters; vol. 28; nb. 26; (1987); p. 3013 - 3014 View in Reaxys

68 %

With 3-(4-methoxyphenyl)-1-((1S,3R)-3-phenyl-1,2,3,4-tetrahydroisoquinolin-1-yl)naphthalen-2-ol in n-heptane, toluene, Time= 72h, T= 0 °C , optical yield given as percent ee MacLeod, Patricia D.; Reckling, Amy M.; Li, Chao-Jun; Heterocycles; vol. 80; nb. 2; (2010); p. 1319 - 1337 View in Reaxys

66 %

With [5-((2S)-1-methylpyrrolidin-2-yl)-2-chloro(4-pyridyl)]bis(2,3,4,5,6-pentafluorophenyl)methan-1-ol in toluene, Time= 24h, T= 0 °C , optical yield given as percent ee Capracotta, Sonja S.; Comins, Daniel L.; Tetrahedron Letters; vol. 50; nb. 16; (2009); p. 1806 - 1808 View in Reaxys

66 %

2 :Example 2: Testing Amino-alcohol Catalysts in the Catalytic Asymmetric Addition of Diethylzinc to Aldehydes. The ligands that "were synthesized and characterized "were screened for use as catalysts in the asymmetric addition of diethylzinc to benzal-

12/258

2018-07-03 17:29:03

dehyde. All reactions were run in toluene and kept at 0° C for 24 h (Table 3).General procedure for the catalytic asymmetric addition of diethylzinc to benzaldehyde. To a stirred solution of the catalyst (0.20 equiv) in toluene (2 mL) at 0 0C was added diethylzinc (1.0 M in hexane, 1.08 mL). After stirring the reaction for 30 min at 0 0C. benzaldehyde (0.05 mL. 0.49 mmol) was added and the reaction was stirred at this temperature for 24 h. The reaction was quenched with an aqueous saturated solution of ammonium chloride (2 mL). and the mixture was extracted with diethyl ether (3 x 5 mL). The combined organic layers were dried over MgSO4. filtered, and concentrated to afford the crude product. Purification by RPLC (10percent EtOAc/hexanes) provided the product as a colorless oil. The ee of the alcohol products was determined by chiral HPLC.(i?)-l-Phenyl-l-propanol (17): [η]31 D +37.8 (c 1.70. CH2C12). 95percent ee by HPLC analysis (Chiralcel OD column. 2percent z-propanol/hexanes. 1.00 mL/min. η = 219 nm). Retention times: R (major) 11.98 min. S (minor) 14.95 min.(if)-l-(4-Chlorophenyl)-l-propanol: [η]31 D +31.5 (c 1.90. CH2C12). 94percent ee by HPLC analysis (Chiralcel OD column, 2percent z-propanol/hexanes. 0.80 mL/min. η = 254 nm). Retention times: R (major) 15.04 min, S (minor) 16.41 min.(i?)-l-(4-Methoxyphenyl)-l-propanol: [η]31 D +28.3 (c 0.70. CH2C12). 94percent ee by HPLC analysis (Chiralcel OD column. 2percent z'-propanol/hexanes. 1.00 mL/min. η = 261 nm). Retention times: R (major) 45.09 min. S (minor) 55.69 min.(i?)-l-Phenyl-3-pentanol: [η]31 D -18.6 (c 1.25. CH2C12). 69percent ee by HPLC analysis (Chiralcel OD column. 5percent z'-propanol/hexanes. 1.00 mL/min. η = 262 nm). Retention times: R (major) 9.14 min. S (minor) 12.94 min.(i?)-l-Phenylpent-l-(E)-en-3-ol: [η]31 D -1.0 (c 2.60. CH2C12): 72percent ee by HPLC analysis (Chiralcel OD column eluted with 5percent z'-propanol/hexanes at 0.80 mL/min and detection at η = 254 nm). Retention times: R (major) 14.97 min, S (minor) 24.68 min.15 93 (5)-l,3-Diphenyl-prop-2-yn-l-ol (93). Diethylzinc (1.0 M in hexane, 0.39 mL) was added dropwise to a solution of 75d (1 1 mg, 0.02 mmol) in toluene (2 mL) at room temperature. After 15 h, phenylacetylene (0.06 mL, 0.41 mmol) was added at room temperature and the reaction was stirred for 1 h. Benzaldehyde (0.02 mL, 0.20 mmol) was then added and the reaction was stirred for 24 h at room temperature. The reaction was quenched with water and extracted with diethyl ether (2 x 5 mL). The combined organic layers were dried over magnesium sulfate, filtered, and concentrated. The crude oil was purified by RPLC (10percent EtOAc/hexanes) to afford 93percent (38 mg) of the product as a colorless oil; 13percent ee determined by HPLC analysis (Chiralcel OD column eluted with 20percent /-propanol/hexanes at 1.00 mL/min and detection at η = 254 nm). Retention times: R (minor) 7.50 min, S (major) 10.48 min.40aToluene proved to be the better solvent for the reaction since a slight decrease in ee to 72percent was observed when catalyst 75a was used in cyclohexane. Conditions where an additive, such as titanium(IV) isopropoxide. were also attempted with catalyst 75a. but both a low yield and low ee's were obtained (4percent and 6percent. respectively). Only results from the standard reaction conditions are shown in Table 14.Both diastereomers of the secondary alcohols were examined as catalysts in the reaction, shown in entries 2-9. Interestingly, only diastereomers with the absolute configuration of 74a-d had a significant effect on the enantioselectivity. In addition, in every case where a significant enatioselectivity was observed, the primary product was the R enantiomer.Compound 74d (entry 9) gave the highest enantiomeric excess for this class of ligands: however, the 1-naphthyl substituted ligand 74c provided a similar ee of 76percent with an 83percent yield. In the case of 74d. the electron-withdrawing effect of the fluorines on the aromatic ring created a decrease in the yield as compared to 74a-c.When comparing the selectivity provided by catalysts 74c and 74d (76percent ee and 79percent ee. respectively) with 74a and 74b (both 64percent ee) it appears that selectivity can be increased by either adding more electron withdrawing substituents or increasing the steric hindrance. These findings were also observed in the series of tertiary alcohols 75a-d. The decafluorobenzophenone tertiary alcohol 75d gave a 95percent ee, while the benzophenone tertiary alcohol 75a only gave 79percent ee (entries 10 and 13). The greater steric bulk of 75b gave an ee of 83percent. while the smaller tertiary alcohol 75c only afforded 66percent ee (entries 11 and 12). Table 3: Secondary and tertiary alcohols as ligands in the catalytic asymmetric addition of diethylzinc to benzaldehydeEt2Zn (2.2 equiv), catalyst (0.2 equiv) toluene. 0 0C, 24 h 15 17"Determined by chiral HPLC on column C hiralcel OD with /. = 219 iim. 10° o ;-pi opanol liexanes a> the eluent with a flow rate of 1.00 niL mm. Lower yield due to difficulties m purificationIn general, the tertiary alcohols, entries 10, 11, and 13. enhanced the selectivity of the reaction more than the secondary alcohols. The decafluoro tertiary alcohol 75d proved to provide one of the best enantioselectivities (95percent ee) overall, but gave the lowest yield.Surprisingly, the increased steric bulk provided by the tert-butyl groups on compound 75c did not improve the selectivity over that afforded by 75d and even decreased the selectivity when compared to the smaller compound 75a. Gau and Wu discovered with their η-amino alcohol systems that aromatic substituents increased the ee, while alkyl substituents decreased the ee (Gau, H. M.; Wu, K. H. Or ganomet allies 2003, 22, 5193-5200). Their finding is consistent with the results in Table 14 when comparing the tertiary and secondary alcohols. For example, the additional phenyl group on 75a (Table 3, entry 10) causes an increase in the selectivity by about 10 percent ee over that of entry 3. This shows that increase in steric bulk of the catalyst does help to increase enantioselectivity. However, catalyst 75b did not seem to show much of an increase in yield or selectivity from 75a suggesting that the 2-naphthyl substituents do not increase the sterics much from the phenyl substituents.Upon determining 75d as the catalyst with the highest selectivity at 20 mol percent, the asymmetric reaction parameters were optimized by varying the conditions of the reaction by lowering the catalyst loading (Table 4). When going from 20 mol percent to 10 mol percent of catalyst 75d, only a slight change in percent yield and percent ee were observed. Much to our delight, the reaction went further to completion when 5 mol percent of catalyst 75d was employed in the reaction than when 10 percent was used. However, when the amount of catalyst was further reduced to 2 mol percent of 75d, a decrease in the yield and selectivity was observed (Table 4, entry 4).Table 4: Variation of the catalyst loading using 75d as the ligand for the diethylzinc addition to benzaldehydeaLo\\ver yield due to difficulties in purification.Using the optimized asymmetric reaction conditions. 75d was used to catalyze the addition of diethylzinc to other aldehyde substrates as shown in Table 5. The -Cl and - OCHs substituents on the aromatic ring did not seem to have a large effect on the enantiocontrol of the reaction (entries 2 and 3) and afforded results similar to benzaldehyde; however, the yield of the reaction was lower with chlorobenzaldehyde as the substrate. When cinnamaldehyde and hydrocinnamaldehyde were employed in the

13/258

2018-07-03 17:29:03

reaction, a decrease in the enantioselectivity was observed.Table 5: Diethylzinc additions to aldehydes catalyzed by 75d (5 mol percent)Overall, the novel nicotine-based decafluorodiphenyl catalyst demonstrates respectable yields and high enantioselectivities when employed in the catalytic asymmetric addition of diethylzinc to aromatic aldehydes. Finally, to investigate the effect of the chlorine substituent on the nicotine-based catalysts during the asymmetric reaction, compounds 9028 and 91 were synthesized and compared to 75a (Schemes 3 and 4). This comparison would provide insight as to whether or not the C-4 substituted nicotine-based compounds could be improved to enhance selectivity in the asymmetric reaction by adding or removing chlorine substituents from the pyridine ring.Scheme 3: Synthesis of 9090Scheme 4: Synthesis of 91Addition of a chlorine substituent to the C-5 position of nicotine, as shown with compound 90, increased the selectivity to 95percent ee at 20 mol percent, but at 5 mol percent a slight decrease in selectivity was observed (Table 6, entries 3 and 4). In contrast, catalyst 91 with no chlorine substituents decreased the selectivity as compared to ligand 75a as seen in Table 6, entries 5 and 6. The selectivity and yield were worse when the amount of catalyst 91 was lowered to 5 mol percent. Therefore, it may be desirable to have at least one chlorine substituent on the nicotine portion of the molecule, in addition to the alcohol functionality off of the C-4 position, in order to maintain adequate selectivity in the asymmetric reaction. Table 6: Comparing catalysts 75a, 75d, 90 and 91 in the asymmetric reaction of diethylzinc and benzaldehydea aReacrioηs were run at 0 ~C for 24 h in toluene.In conclusion, the more sterically hindered C-4 tertiary alcohols of (ηS)-6-chloronicotine provided better enantio selectivity than the C-4 secondary alcohols. Additionally, electron withdrawing fluorines on the aromatic ring improved the ee as compared to electron donating groups, as seen when comparing catalyst 75d with 75a and 75c. The effect of the chlorines on the pyridine ring of nicotine also proved to be beneficial when applied to the asymmetric reaction. Two chlorine substituents on nicotine derivative 90 proved to be superior to only one chlorine substituent on molecule 75a. When no chlorines were on C-4 substituted 91, the yield and the selectivity decreased noticeably.Overall, compound 75d provided the most promising results, yielding an ee of 95percent when benzaldehyde was the substrate and only 5 mol percent of the catalyst was used. The catalyst also provided acceptable results when other substrates were employed in the asymmetric reaction.However, compound 75d with zinc(II) triflate yielded very little product was obtained (data not shown). The diethylzinc conditions were applied where the product 93 was obtained with a 93percent yield with a 13percent ee, but some ethylphenyl alcohol 17 was also observed. In addition, when applied to the Henry reaction, the yields were very low (data not shown). Stage 1: With [5-((2S)-1-methylpyrrolidin-2-yl)-2-chloro(4-pyridyl)]bis(2,3,4,5,6-pentafluorophenyl)methan-1-ol in hexane, toluene, Time= 0.5h, T= 0 °C Stage 2: in hexane, toluene, Time= 24h Stage 3: With water, ammonium chloride in hexane, toluene Patent; NORTH CAROLINA STATE UNIVERSITY; COMINS, Daniel, L.; CAPRACOTTA, Sonja, S.; WO2010/40059; (2010); (A1) English View in Reaxys 64 %

With dendritic chiral catalyst in toluene, T= 20 °C , Alkylation Sato, Itaru; Shibata, Takanori; Ohtake, Koji; Kodaka, Ryo; Hirokawa, Yutaka; Shirai, Nobuaki; Soai, Kenso; Tetrahedron Letters; vol. 41; nb. 17; (2000); p. 3123 - 3126 View in Reaxys

24 %

With (R)-N,N,N',N'-tetrabutyl-2,2'-dihydroxy-1,1'-binaphthyl-3,3'-dicarboxamide in tetrahydrofuran, hexane, Time= 15h, T= 0 °C Kitajima, Hiroshi; Ito, Katsuji; Aoki, Yuko; Katsuki, Tsutomu; Bulletin of the Chemical Society of Japan; vol. 70; nb. 1; (1997); p. 207 - 217 View in Reaxys With 4S,5R-3,4-Me-5-Phe-1,3,2-oxazaborolidine in toluene, T= 0 °C , further catalysts, Product distribution Joshi, N. N.; Srebnik. M.; Brown, Herbert C.; Tetrahedron Letters; vol. 30; nb. 41; (1989); p. 5551 - 5554 View in Reaxys With chiral <(CH3)2NCH(CH3)CH(Ph)S>2 in toluene, Time= 20h, Ambient temperature, var. chiral sulfur derivative of ephedra alkaloids, Product distribution, Mechanism Hof; Poelert; Peper; Kellogg; Tetrahedron Asymmetry; vol. 5; nb. 1; (1994); p. 31 - 34 View in Reaxys With (4S,5R)-3,4-dimethyl-5-phenyl-1,3,2-oxazaborolidine in toluene, Time= 30h, T= -25 °C Joshi, N. N.; Srebnik. M.; Brown, Herbert C.; Tetrahedron Letters; vol. 30; nb. 41; (1989); p. 5551 - 5554 View in Reaxys

14/258

2018-07-03 17:29:03

With (1R,2'S)-phenyl(1-neopentylpyrrolidin-2-yl)methanol, 1.) hexane, reflux, 20 min, 2.) hexane, Yield given. Multistep reaction Soai, Kenso; Ookawa, Atsuhiro; Kaba, Tatsuya; Ogawa, Kazuo; Journal of the American Chemical Society; vol. 109; nb. 23; (1987); p. 7111 - 7115 View in Reaxys With (1R,3R,5R)-3-(diphenylhydroxymethyl)-2-azabicyclo<3.3.0>octane, 1.) toluene, from -20 deg C to RT, 2.) toluene, RT, 48 h, Multistep reaction Wallbaum, Sabine; Martens, Juergen; Tetrahedron: Asymmetry; vol. 4; nb. 4; (1993); p. 637 - 640 View in Reaxys With n-octyne, (S)-(-)-2-<2',2'-dimethyl-1'-(2''-pyridyl)propoxy>-1,1-di-(η-naphthyl)ethanol, 1.) THF, reflux, 2.) RT, 2 h, Yield given. Multistep reaction Ishizaki, Miyuki; Hoshino, Osamu; Tetrahedron: Asymmetry; vol. 5; nb. 10; (1994); p. 1901 - 1904 View in Reaxys in hexane, Time= 12.5h, Ambient temperature, chiral diselenide catalyst Wirth, Thomas; Tetrahedron Letters; vol. 36; nb. 43; (1995); p. 7849 - 7852 View in Reaxys With titanium(IV) isopropylate, polymer-bound TADDOL in toluene, Time= 16h, T= -30 °C , Yield given Seebach, Dieter; Marti, Roger E.; Hintermann, Tobias; Helvetica Chimica Acta; vol. 79; nb. 6; (1996); p. 1710 - 1740 View in Reaxys With (2S,3R,4S)-N-methyl-4-hydroxy-3-methoxymethyloxy-2-trityloxymethylpyrrolidine in hexane, cyclohexane, Time= 20h, T= 0 °C , Yield given Ikota, Nobuo; Inaba, Hiroko; Chemical and Pharmaceutical Bulletin; vol. 44; nb. 3; (1996); p. 587 - 589 View in Reaxys With (R)-N,N,N',N'-tetra-isopropyl-2,2'-dihydroxy-1,1'-binaphthyl-3,3'-dicarboxamide, 1.) hexane, THF, -23 deg C, 15 min, 2.) hexane, THF, 0 deg C, 24 h, Yield given. Multistep reaction Kitajima, Hiroshi; Ito, Katsuji; Katsuki, Tsutomu; Chemistry Letters; nb. 5; (1996); p. 343 - 344 View in Reaxys With (R)-2-<(4S,7R)-7,8,8-trimethyl-4,5,6,7-tetrahydro-4,7-methano-1-indazolyl>-1-phenylethanol, 1) toluene, hexane, -15 deg C, 15 min; 2) toluene, hexane, rt, 2 d; further reagents, Yield given. Multistep reaction Kotsuki, Hiyoshizo; Wakao, Masahiro; Hayakawa, Hiroyuki; Shimanouchi, Tomoyasu; Shiro, Motoo; Journal of Organic Chemistry; vol. 61; nb. 25; (1996); p. 8915 - 8920 View in Reaxys With (all-R)-1'-(1-methyl-octahydro-cyclopenta<b>pyrrole-2-yl)cyclopentanol, 1.) toluene, -40 deg C, 30 min, 2.) toluene, 22 deg C, 40 h, Yield given. Multistep reaction Wilken, Joerg; Kossenjans, Michael; Groeger, Harald; Martens, Juergen; Tetrahedron Asymmetry; vol. 8; nb. 12; (1997); p. 2007 - 2015 View in Reaxys 98 % Chromat.

With chiral o-hydroxynaphthyldiazaphosphpholidine oxide in tetrahydrofuran, hexane, Time= 48h, Ambient temperature Legrand, Olivier; Brunel, Jean-Michel; Buono, Gerard; Tetrahedron Letters; vol. 39; nb. 51; (1998); p. 9419 - 9422 View in Reaxys With (S)-(-)-1-benzyl-2-(1-hydroxy-1-methylethyl)-pyrrolidine, 1.) hexane, benzene, 0 deg C, 0.5 h, 2.) hexane, benzene, from 0 deg C to RT, 12 h, Yield given, Multistep reaction Yang, Xiaowu; Shen, Jianheng; Da, Chaoshan; Wang, Rui; Choi, Michael C. K.; Yang, Liwei; Wong, Kwok-Yin; Tetrahedron Asymmetry; vol. 10; nb. 1; (1999); p. 133 - 138 View in Reaxys

15/258

2018-07-03 17:29:03

With <CH3-CH(S)-NMe2-C6H4-2-Me3Si-6-Se>2 in toluene, T= -15 °C Santi, Claudio; Wirth, Thomas; Tetrahedron Asymmetry; vol. 10; nb. 6; (1999); p. 1019 - 1023 View in Reaxys 100 % Chromat.

With chiral o-hydroxyaryldiazaphosphonamide in tetrahydrofuran, hexane, Time= 48h, T= 20 °C , Addition Legrand, Olivier; Brunel, Jean-Michel; Buono, Gerard; Tetrahedron Letters; vol. 41; nb. 13; (2000); p. 2105 - 2109 View in Reaxys

1800 %

With chiral 1,4-aminoalcohol in toluene, Time= 2h, T= 20 °C , pH= 6, Addition, Title compound not separated from byproducts Hanyu, Naoto; Aoki, Tasuku; Mino, Takashi; Sakamoto, Masami; Fujita, Tsutomu; Tetrahedron Asymmetry; vol. 11; nb. 14; (2000); p. 2971 - 2979 View in Reaxys

100 % Spectr.

With erythro Bu2NCH(CH3)CH(OH)(Ferrocene) in toluene, Time= 1h, T= 20 °C , Alkylation, Product distribution, Further Variations: Catalysts, Temperatures Bastin; Brocard; Pelinski; Tetrahedron Letters; vol. 41; nb. 38; (2000); p. 7303 - 7307 View in Reaxys With (1S,2R)-1-phenyl-2-(piperidin-1-yl)-3-(trityloxy)propane-1-thiol in hexane, toluene, Time= 5h, T= 0 °C Jimeno; Moyano; Pericas; Riera; Synlett; nb. 7; (2001); p. 1155 - 1157 View in Reaxys With bis-L-proline-o-C6H4(CH2)2 in toluene, T= 0 °C , Product distribution, Further Variations: Reagents Xu, Qianyong; Wang, Hui; Pan, Xinfu; Chan, Albert S.C; Yang, Teng-Kuei; Tetrahedron Letters; vol. 42; nb. 35; (2001); p. 6171 - 6173 View in Reaxys With poly(binaphthyl zinc-salen complex) in tetrahydrofuran, T= -60 °C Furusho, Yoshio; Maeda, Takeshi; Takeuchi, Takeshi; Makino, Nobuaki; Takata, Toshikazu; Chemistry Letters; nb. 10; (2001); p. 1020 - 1021 View in Reaxys

100 % Spectr.

Stage 1: With titanium(IV) isopropylate, (1R,2S)-2-(4-methylbenzenesulfonylamino)-1,3-diphenyl-1-propanol in hexane, dichloromethane, Time= 0.5h, T= 0 °C Stage 2: in dichloromethane, Time= 12h, T= 0 °C You, Jing-Song; Shao, Ming-Yuan; Gau, Han-Mou; Tetrahedron Asymmetry; vol. 12; nb. 21; (2001); p. 2971 - 2975 View in Reaxys

97 % Chromat.

With (2R,3R)-(1-benzyl-3-phenylazetidin-2-yl)diphenylmethanol in toluene, Time= 24h, T= 20 °C Couty, Francois; Prim, Damien; Tetrahedron Asymmetry; vol. 13; nb. 23; (2002); p. 2619 - 2624 View in Reaxys

98 % Chromat.

With (S)-(-)-3-propyl-1-phenyl-2-piperidinohexan-3-ol in hexane, Time= 5h, T= 0 °C Da, Chao-Shan; Han, Zhi-jian; Ni, Ming; Yang, Fan; Liu, Da-Xue; Zhou, Yi-Feng; Wang, Rui; Tetrahedron Asymmetry; vol. 14; nb. 6; (2003); p. 659 - 665 View in Reaxys

93 % Chromat.

With di((2S)-2-(t-butoxycarbonylamino)-3-phenylpropyl) diselenide in toluene, Time= 24h, T= 20 °C Braga, Antonio L.; Paixao, Marcio W.; Luedtke, Diogo S.; Silveira, Claudio C.; Rodrigues, Oscar E. D.; Organic Letters; vol. 5; nb. 15; (2003); p. 2635 - 2638 View in Reaxys Stage 1: With (3R,4S)-2,5-dimethyl-4-(pyrrolidin-1-yl)hexane-3-thiol in toluene, Time= 0.333333h, T= 20 °C Stage 2: in toluene, Time= 12h, T= -20 °C Tseng, Shi-Liang; Yang, Teng-Kuei; Tetrahedron Asymmetry; vol. 15; nb. 21; (2004); p. 3375 - 3380

16/258

2018-07-03 17:29:03

View in Reaxys With C6H5(R)-CH(SCN)(S)-CH(CH3)N(CH2CH2CH2CH3)2 in hexane, Time= 3h, T= 20 °C , Product distribution, Further Variations: Reagents, Solvents, reaction times Jin, Myung-Jong; Kim, Young-Mok; Lee, Kyoung-Soo; Tetrahedron Letters; vol. 46; nb. 15; (2005); p. 2695 - 2696 View in Reaxys 96 % Chromat.

With (Ra)-3,3'-di(3-hexyloxy-2-pyridyl)-2,2'-HO-1,1'-binaphthyl in tetrahydrofuran, Time= 2h, T= 0 °C Milburn, Robert R.; Hussain, S. M. Shakil; Prien, Olaf; Ahmed, Zaheer; Snieckus, Victor; Organic Letters; vol. 9; nb. 22; (2007); p. 4403 - 4406 View in Reaxys

74 %Chromat.

Stage 1: With N,N'-[(2η-hydroxy)pinan-3-ylidene]ethane-1,2-diamine in hexane, toluene, Time= 0.0833333h Stage 2: in hexane, toluene, Time= 20h, T= 20 °C Stage 3: With ammonium chloride in hexane, water, toluene, optical yield given as percent ee, enantioselective reaction Salehi, Peyman; Dabiri, Minoo; Kozehgary, Gholamreza; Baghbanzadeh, Mostafa; Tetrahedron Asymmetry; vol. 20; nb. 22; (2009); p. 2609 - 2611 View in Reaxys

95 %Chromat.

With (1R,2R)-N,N'-dimethyl-N,N'-bis{[(1S,2R,4R)-7,7-dimethyl-2-hydroxynorborn-1-yl]carbonyl}cyclohexane-1,2-diamine in Petroleum ether, Time= 5h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction De Las Casas Engel, Tomas; Maroto, Beatriz Lora; De La Moya Cerero, Santiago; European Journal of Organic Chemistry; nb. 9; (2010); p. 1717 - 1727 View in Reaxys

9 %Chromat.

Stage 1: With C18H16N2 in tetrahydrofuran, hexane, Time= 30h, T= 0 °C Stage 2: With water, ammonium chloride in tetrahydrofuran, hexane, Saturated solution, optical yield given as percent ee, enantioselective reaction Qi, Gao; Judeh, Zaher M.A.; Tetrahedron Asymmetry; vol. 21; nb. 4; (2010); p. 429 - 436 View in Reaxys With titanium(IV) isopropylate in hexane, dichloromethane, T= 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Liu, Xiao; Wang, Peiyuan; Zhang, Lei; Yang, Jie; Li, Can; Yang, Qihua; Chemistry - A European Journal; vol. 16; nb. 42; (2010); p. 12727 - 12735 View in Reaxys 4.4. Typical procedure for the addition of diethylzinc to aldehyde General procedure: To a solution of chiral ligand 1 (0.05 mmol) dissolved in dry hexane (1 mL), Et2Zn (2 mL, 1 M solution in hexane) was added at room temperature under a nitrogen atmosphere. Then the mixture was stirred for 1 h at room temperature. After the mixture was cooled to -30 °C aryl aldehyde (1 mmol in 1 mL in hexane) was added. After 24 h stirring at -30 °C under a nitrogen atmosphere, the reaction was quenched with saturated ammonium chloride solution, extracted with DCM (2 .x. 50 mL), washed with brine (2 .x. 25 mL), and dried with anhydrous Na2SO4. The solvent was removed under reduced pressure, and the conversion and yield were determined by 1H NMR analysis with bromoform as an internal standard directly on the crude mixture. Stage 1: With (2S)-3-ethyl-2-(octahydro-2H-4,7-ethanoisoindol-2-yl)-1-phenylpentan-3-ol in hexane, Time= 24h, T= -30 °C , Inert atmosphere Stage 2: With ammonium chloride in hexane, optical yield given as percent ee, enantioselective reaction Sahin, Engin; Kilic, Hamdullah; Tetrahedron Asymmetry; vol. 22; nb. 3; (2011); p. 277 - 282 View in Reaxys With titanium(IV) isopropylate in dichloromethane, Time= 4h, T= 0 °C , optical yield given as percent ee, enantioselective reaction Liu, Xiao; Wang, Peiyuan; Yang, Yan; Wang, Peng; Yang, Qihua; Chemistry - An Asian Journal; vol. 5; nb. 5; (2010); p. 1232 - 1239 View in Reaxys

17/258

2018-07-03 17:29:03

With C31H29NO in hexane, toluene, Time= 15h, T= 0 - 20 °C , enantioselective reaction Zhuravsky, Roman P.; Danilova, Tatiana I.; Antonov, Dmitrii Yu.; Sergeeva, Elena V.; Starikova, Zoya A.; Godovikov, Ivan A.; Il'In, Michail M.; Rozenberg, Valeria I.; Israel Journal of Chemistry; vol. 52; nb. 1-2; (2012); p. 156 - 170 View in Reaxys 98 %Chromat.

Stage 1: With N,N'-bis{[(1S,2R,4R)-7,7-dimethyl-2-hydroxynorborn-1-yl]carbonyl}homopiperazine in hexane, Time= 1h, T= 20 °C , Inert atmosphere Stage 2: With hydrogenchloride in hexane, water, Inert atmosphere, enantioselective reaction De Las Casas Engel, Tomas; Sanchez-Carnerero, Esther M.; Gallardo-Araya, Claudio M.; Jimenez, Florencio Moreno; Maroto, Beatriz Lora; De La Moya Cerero, Santiago; Sokolovskaya, Ekaterina; Chirality; vol. 24; nb. 10; (2012); p. 771 777,7 View in Reaxys 4.11. Typical procedure for the addition of diethylzinc to aldehyde General procedure: To a solution of 4 (0.05 mmol) in freshly distilled diethyl ether(1 mL) diethylzinc (1 mL of 1 M hexane solution, 1 mmol) was added at ambient temperature under argon. The mixture was stirredfor 1 h and then cooled to 15 C. A solution of aldehyde (0.5 mmol) in diethyl ether (1 mL) was added via syringe and the mixture was stirred for 48 h. The reaction was then quenched bythe addition of saturated NH4Cl solution (4 mL), and diphenylmethane (0.25 mmol) was added as an internal standard. The mixture was extracted with EtOAc (3 10 mL) and the combined organic extracts were washed with water (10 mL) and brine (10 mL). The organic layer was dried over anhydrous Na2SO4 and concentrated in vacuo. Conversion and yield were determined from the crude mixture by 1H NMR analysis. The crude product was purified by preparative thin layer chromatography on silica gel (hexane/EtOAc,90:10) and the enantiomeric excess of the addition product was determined by GC on a Chiral b-DEX 120 capillary column.11b With 2-[(1S)-1-hydroxyethyl]-3-{(3R)-3-[(1R)-1-hydroxyethyl]-2,2-dimethylaziridin-1-yl}quinazolin-4(3H)-one in diethyl ether, hexane, Time= 48h, T= -15 °C , Inert atmosphere, Temperature, Time, enantioselective reaction Celik, Saffet; Cakici, Murat; Kilic, Hamdullah; Sahin, Ertan; Tetrahedron Asymmetry; vol. 26; nb. 2-3; (2015); p. 152 - 157 View in Reaxys

99 %Chromat.

4.6. General procedure for enantioselective alkylations General procedure: To the chiral ligand (0.15 mmol) and aldehyde (1 mmol) in an inert atmosphere, 4 mL of dry cyclohexane were added. The temperature of the reaction mixture was lowered to 0°C and diethylzinc (2 mmol, 2 mL, as a 1 M hexane solution) was added. The reaction was stirred 10 min at 0°C and then for 24 h at the required temperature. Subsequently, a saturated ammonium chloride solution (1 mL) was added, followed by 2 M HCl (1 mL) and the reaction mixture was extracted with diethyl ether. The joint organic phases were washed with water and brine and dried over anhydrous sodium sulfate. The resulting solution was analyzed by GC on a chiral η-cyclodextrin capillary column in order to determine the ee of the products.24 With (S)-methyl 2,2-diethyl-5,5-dimethyl-1,3-thiazolidine-4-carboxylate in hexane, cyclohexane, Time= 24.1667h, T= 0 - 20 °C , Inert atmosphere, Schlenk technique, Reagent/catalyst, enantioselective reaction Serra, M. Elisa Silva; Costa, Dora; Murtinho, Dina; Tavares, Nélia C.T.; Pinho e Melo, Teresa M.V.D.; Tetrahedron; vol. 72; nb. 39; (2016); p. 5923 - 5927 View in Reaxys With Ti modified chiral porous covalent organic framework (S,S)-CCOF-1 in hexane, toluene, Time= 10h, T= -30 °C , Inert atmosphere, enantioselective reaction Wang, Xiuren; Han, Xing; Zhang, Jie; Wu, Xiaowei; Liu, Yan; Cui, Yong; Journal of the American Chemical Society; vol. 138; nb. 38; (2016); p. 12332 - 12335 View in Reaxys

97 %Chromat.

Stage 1: With C26H42N2O5 in hexane, Time= 0.5h, T= 20 °C , Inert atmosphere Stage 2: in hexane, Time= 1h, T= 20 °C , Inert atmosphere, Reagent/catalyst, enantioselective reaction Sánchez-Carnerero, Esther M.; Sandoval-Torrientes, Rafael; Urieta-Mora, Javier; Moreno, Florencio; Maroto, Beatriz L.; de la Moya, Santiago; Reactive and Functional Polymers; vol. 113; (2017); p. 23 - 30 View in Reaxys

18/258

2018-07-03 17:29:03

H (v2)

H O

Rx-ID: 2681717 View in Reaxys 2/176 Yield 99 %

Conditions & References With titanium(IV) isopropylate, methyl 4,6-O-PhCH-2-deoxy-2-p-TsNH-η-D-glucopyranoside in dichloromethane, toluene, Time= 3h, T= 20 °C , Product distribution, Further Variations: Catalysts, Temperatures, amounts of catalyst; reaction times Bauer, Tomasz; Tarasiuk, Joanna; Paniczek, Konrad; Tetrahedron Asymmetry; vol. 13; nb. 1; (2002); p. 77 - 82 View in Reaxys

97 %

Stage 1: in toluene, Time= 10h, T= 0 °C Stage 2: in toluene, Time= 38h, T= 20 °C , Catalytic behavior, Reagent/catalyst, Temperature, enantioselective reaction Zhao, Wen-Xian; Liu, Nian; Li, Gao-Wei; Chen, Dong-Li; Zhang, An-An; Wang, Min-Can; Liu, Lantao; Green Chemistry; vol. 17; nb. 5; (2015); p. 2924 - 2930 View in Reaxys

93 %

With 1-[(S)-4-isopropyl-5,5-dimethyloxazolinyl]-2(Rp)-(diphenylmethanol)ferrocene in hexane, Time= 0.333333h, T= -20 °C , Schlenk technique, Inert atmosphere, Temperature, Solvent Nottingham, Chris; Benson, Robert; Müller-Bunz, Helge; Guiry, Patrick J.; Journal of Organic Chemistry; vol. 80; nb. 20; (2015); p. 10163 - 10176 View in Reaxys

91 %

With N-{(1S,2S)-2-[(dimethylamino)methyl]cyclohexyl}-4-methylbenzenesulfonamide in hexane, toluene, Time= 24h, T= 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Hirose, Takuji; Sugawara, Kazuyuki; Kodama, Koichi; Journal of Organic Chemistry; vol. 76; nb. 13; (2011); p. 5413 - 5428 View in Reaxys

90 %

With (1S,2R)-N-benzyl-N-methylephedrinium chloride in hexane, Time= 72h, other aldehydes, var. solvents, var. times; other (1S,2R)-N-benzyl-N-methylephedrinium halides as catalysts of enantioselective reaction of aldehydes, Product distribution Soai, Kenso; Watanabe, Masami; Journal of the Chemical Society, Chemical Communications; nb. l; (1990); p. 43 - 44 View in Reaxys

90 %

9 :The bisimidate ligands were further tested in 1,2-additions of diethylzinc to benzaldehyde. Amino-alcohols are the ligands of choice in this type of reaction. It is known that bisoxazolines without a hydroxyl substituent give low enantioselectivities. (Ref. 7)A typical procedure is as follows: Bisimidate (IIb) (6.0 mg, 0.012 mmol) was dissolved in toluene (2 mL). Et2Zn (0.75 mL, 1 M in hexane) was added and the resulting yellow solution was stirred for 20 min at room temperature under argon atmosphere. Next, benzaldehyde X (50 μL, 0.49 mmol) was added and the reaction mixture was stirred for another 24 h. The reaction was quenched with 1 mL saturated NH4Cl solution. The reaction mixture was poured in H2O (25 mL) and extracted with EtOAc (3.x.25 mL). The combined organic phases were dried over Na2SO4 and evaporated in vacuo. Purification by flash chromatography over silica gel (pentane/EtOAc, 90/10) resulted in XI, 55.7 mg (83percent, 75percent ee). With C12H24N4 in dichloromethane, toluene, Time= 3h, T= 20 °C , Inert atmosphere Patent; Noël, Timothy; Vandyck, Koen; Van Der Eycken, Johan; US2012/77989; (2012); (A1) English View in Reaxys

89 %

With titanium(IV) isopropylate, (R)-FBINOL in hexane, toluene, Time= 2h, T= 0 °C , Alkylation Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Curran, Dennis P.; Tetrahedron Letters; vol. 41; nb. 1; (2000); p. 57 60 View in Reaxys

89 %

Stage 1: With N-(5,8-bismethoxymethoxy-2-methyl-1,2-dihydronaphthalen-1-yl)-4-methylbenzenesulfonate in hexane, ethyl acetate, Time= 1h, T= 20 °C , Inert atmosphere

19/258

2018-07-03 17:29:03

Stage 2: in hexane, ethyl acetate, Time= 24h, T= 30 °C , optical yield given as percent ee Yoshida, Kazuhiro; Toyoshima, Takeharu; Akashi, Naohisa; Imamoto, Tsuneo; Yanagisawa, Akira; Chemical Communications; nb. 20; (2009); p. 2923 - 2925 View in Reaxys 88 %

With hydroxymethylphenyl N-(S)-prolinylmethylphenyl sulfoxide in toluene, Time= 24h, Reagent/catalyst Chrzanowski, Jacek; Rachwalski, Michal; Pieczonka, Adam M.; Leniak, Stanislaw; Drabowicz, Jzef; Kielbasiski, Piotr; Tetrahedron; vol. 72; nb. 21; (2016); p. 2649 - 2655 View in Reaxys

87 %

With Ar(S,R,ηR,η'S)CrCO3 in toluene, Time= 18h, T= 0 °C , Yields of byproduct given Uemura, Motokazu; Miyake, Ryuta; Hayashi, Yuji; Journal of the Chemical Society, Chemical Communications; nb. 23; (1991); p. 1696 - 1697 View in Reaxys

83 %

With (R,R)-6,6'-bis(2,2-dimethyl-1-hydroxypropyl)-2,2'-bipyridine in hexane, toluene, Time= 3h, T= 0 °C , Yields of byproduct given. Title compound not separated from byproducts Bolm, Carsten; Schlingloff, Gunther; Harms, Klaus; Chemische Berichte; vol. 125; nb. 5; (1992); p. 1191 - 1204 View in Reaxys

83 %

Chiral catalysts 9b(0.1 mmol) and benzene (10 mL) were placed in a flask. To ensure dryness, 5 mLof benzene were distilled off. The mixture was cooled to 0°C and a solution ofdiethylzinc (1.0 M solution in hexane, 3 mmol) was added under an argon atmosphere. Afterstirring for 0.5 h, an benzaldehyde (1 mmol) was added at 0°Cand the mixture was stirred at room temperature for 12 h. After this time, a 5percentaqueous solution of hydrochloric acid was added to the mixture. Both layerswere separated and the aqueous layer was extracted with diethyl ether (4x). Thecombined organic layers were washed with brine (10 mL) and dried over MgSO4.The solvents were evaporated to give the crude alcohol, which was purified bypreparative TLC (ethyl acetate/ hexane 1:7) (yield 83percent, 75percent ee).1H NMR (CDCl3):η 0.94 (t, J = 7.4 Hz, 3H), 1.69–2.06 (m, 2H), 2.0 (br s, 1H), 4.59(t, J = 6.59 Hz, 1H),7.25–7.45 (m, 5H) [1]. [η]D = +33.7 (R)Column: Lux 5μ Cellulose – 1 (Phenomenex)Solvent: Hexane :Isopropanol (70:30)η = 254 nm With C19H23NO3S in hexane, toluene, T= 0 - 20 °C , Inert atmosphere, Reagent/catalyst Chrzanowski, Jacek; Rachwalski, Michal; Pieczonka, Adam M.; Leniak, Stanislaw; Drabowicz, Jzef; Kielbasiski, Piotr; Tetrahedron; vol. 72; nb. 21; (2016); p. 2649 - 2655 View in Reaxys

81 %

With Zn(II) complex with chiral Lewis acid-Lewis base ligand in toluene, Time= 3h, T= 20 °C Casarotto, Virginie; Li, Zhongtao; Boucau, Julie; Lin, Yun-Ming; Tetrahedron Letters; vol. 48; nb. 31; (2007); p. 5561 5564 View in Reaxys

81 %

4.6. Addition of diethylzinc on aryldehydes General procedure: 4.6.1. General procedure. In an oven-dried 5 mL flask under argon atmosphere, the ligand (0.1 equiv, 0.1 mmol) was dissolved in 2.5 mL of anhydrous toluene and diethylzinc (1.5 M in toluene, 2 mmol) was added dropwise. The solution was cooled to 0 °C for 15 min and the aldehyde (1 equiv, 1 mmol) was added as a single portion. The mixture was then warmed to room temperature and stirred for 48 h before 1 N HCl was added. The resulting alcohol was extracted with three portions of EtOAc. The organic layers were then combined, washed with brine, dried with Na2SO4, and concentrated in vacuo, giving an oil from which conversion and enantiomeric excess were determined by GC. In one case involving benzaldehyde and ligand 23a (Table 3, entry 1), the crude product was purified by flash chromatography (5:95 EtOAc/hexanes), giving 81percent isolated yield of 32. Commercially available (S)-1-phenyl-1-propanol was used for enantiomer identification on the GC chromatograms. Products 33 and 35, as control experiments, were also prepared from Grignard addition reactions and analyzed by GC. Stage 1: With (2S,5S)-1,4-dimethyl-2,5-bis(phenylmethyl)piperazine in toluene, Time= 0.25h, T= 0 °C , Inert atmosphere Stage 2: in toluene, Time= 48h, T= 0 - 20 °C , Inert atmosphere, enantioselective reaction Bérubé, Christopher; Cardinal, Sébastien; Boudreault, Pierre-Luc; Barbeau, Xavier; Delcey, Nicolas; Giguère, Martin; Gleeton, Dave; Voyer, Normand; Tetrahedron; vol. 71; nb. 42; (2015); p. 8077 - 8084 View in Reaxys

20/258

2018-07-03 17:29:03

75 %

Stage 1: With ((1R,3S)-2,2-dimethyl-3-(1,3-dithian-2-yl)cyclopropyl)diphenylmethanol in toluene, Time= 0.333333h, T= 0 °C , Inert atmosphere, Schlenk technique Stage 2: in toluene, Time= 72h, T= 0 °C , Inert atmosphere, Schlenk technique, Solvent, Temperature, Time, enantioselective reaction Na, Risong; Wang, Bo; Liu, Honglei; Bian, Qinghua; Zhong, Jiangchun; Wang, Min; Guo, Hongchao; Letters in Organic Chemistry; vol. 9; nb. 9; (2012); p. 622 - 627 View in Reaxys

28 %

With 4-methyl-N-{[(1S,2S)-2-(piperidin-1-yl)cyclohexyl]methyl}benzenesulfonamide in toluene, Time= 24h, T= 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Hirose, Takuji; Sugawara, Kazuyuki; Kodama, Koichi; Journal of Organic Chemistry; vol. 76; nb. 13; (2011); p. 5413 - 5428 View in Reaxys Ambient temperature, catalytic asymmetric alkylation in the presence of N-iso-propylephedrine; various conditions and further aldehydes investigated, Product distribution, Mechanism Chaloner, Penny A.; Langadianou, Eugenia; Tetrahedron Letters; vol. 31; nb. 36; (1990); p. 5185 - 5188 View in Reaxys With chiral N-alkylnorephedrine immobilized on (3-chloropropyl)silyl-functionalized alumina gel in hexane, Time= 120h, T= 0 °C , enantioselective Addition; other temp. other time, other solvent; competion rctn. with other n-alkylzincs; N-alkylnorephedrine, immobilized on silica gel or on silica gel coated with poylstyrene, Product distribution Soai, Kenso; Watanabe, Masami; Yamamoto, Atsuhiro; Journal of Organic Chemistry; vol. 55; nb. 16; (1990); p. 4832 - 4835 View in Reaxys With amino alcohol 1 in hexane, toluene, Time= 6h, T= 0 °C , other catalysts, other order of addition of the reagents, other solvent, other temp., also with dimethylzinc, Product distribution Itsuno, Shinichi; Sakurai, Yoshiki; Ito, Koichi; Maruyama, Toshihiro; Nakahama, Seiichi; Frechet, J. M. J.; Journal of Organic Chemistry; vol. 55; nb. 1; (1990); p. 304 - 310 View in Reaxys With (S)-2-amino-4-methylpentan-1-ol in toluene, Time= 43h, T= 20 °C , variation of chiral catalyst, Product distribution Oguni, Nobuki; Omi, Takao; Tetrahedron Letters; vol. 25; nb. 26; (1984); p. 2823 - 2824 View in Reaxys With titanium(IV) isopropylate in hexane, toluene, Time= 12h, Ambient temperature, different dialkylzinc compounds, various temperatures, reaction times and chiral sulfonamide catalysts, Product distribution, Mechanism Yoshioka, Masato; Kawakita, Takashi; Ohno, Masaji; Tetrahedron Letters; vol. 30; nb. 13; (1989); p. 1657 - 1660 View in Reaxys With bornane tridentate ligand in hexane, T= 0 °C , effect of catalysts, concentrations, solvents, temperature and reaction time, examination of further aldehydes and zinc compounds, competitive reaction with (C2D5)2Zn, Product distribution, Mechanism Oppolzer, Wolfgang; Radinov, Rumen N.; Tetrahedron Letters; vol. 29; nb. 44; (1988); p. 5645 - 5648 View in Reaxys With dilithium salt of (2S,5S)-2, 5-diisopropylpiperazine, multistep reaction: enantioselective addition of dialkylzincs catalysed by chiral piperazins; other solvent, temperature, catalysts; other substrates, reactants, Product distribution Niwa, Seiji; Soai, Kenso; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); (1991); p. 2717 - 2720 View in Reaxys With (1R,2S)-N-isopropyl-N-methylnorephedrine in toluene, Time= 48h, Ambient temperature, other catalysts, other temperature, other substrates, other reactants; enantioselectivity, Product distribution Chaloner, Penny A.; Langadianou, Eugenia; Perera, S. A. Renuka; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); (1991); p. 2731 - 2735 View in Reaxys

21/258

2018-07-03 17:29:03

With (2R,5S)-2-(diphenylhydroxymethyl)-3-phenyl-1,3-diazabicyclo<3.3.0>octane in hexane, cyclohexane, Time= 15h, Ambient temperature, other solvent, other reaction time, other temperatur, other amounts of chiral-catalyst, enantioselectivity, Product distribution Asami, Masatoshi; Inoue, Seiichi; Chemistry Letters; nb. 4; (1991); p. 685 - 688 View in Reaxys With (2R,3R)-4-dimethylamino-3-methyl-1,2-diphenyl-butan-2-ol in toluene, Time= 16h, Ambient temperature, effect of aminoalcohol and alkaloid catalysts, reaction temperature and time upon enantioselective addition, Product distribution Muchow, G.; Vannoorenberghe, Y.; Buono, G.; Tetrahedron Letters; vol. 28; nb. 49; (1987); p. 6163 - 6166 View in Reaxys With polymer-bound (1R,2S)-(-)-ephedrine in hexane, Time= 48h, Ambient temperature, other aldehydes, Product distribution Soai, Kenso; Niwa, Seiji; Watanabe, Masami; Journal of Organic Chemistry; vol. 53; nb. 4; (1988); p. 927 - 928 View in Reaxys With polymer-bound chiral amino alcohols in toluene, Time= 62h, T= 0 °C , other chiral amino alcohols, var.aldehydes, var. reaction times, Mechanism, Product distribution Itsuno, Shinichi; Frechet, Jean M.J.; Journal of Organic Chemistry; vol. 52; nb. 18; (1987); p. 4140 - 4142 View in Reaxys With (1S,2R)-N,N-dimethyl-1,2-(9,10-dihydro-9,10-anthraceno)-2-aminoethanol in toluene, Ambient temperature, other aldehyde, other sterically constrained 2-aminoalcohols, Product distribution Kimura; Sugiyama; Ishizuka; Kunieda; Tetrahedron Letters; vol. 33; nb. 22; (1992); p. 3147 - 3150 View in Reaxys With titanium(IV) isopropylate, N,N’-(1R,2R)-cyclohexane-1,2-diylbis(1,1,1-trifluoromethanesulfonamide) in hexane, toluene, Time= 2h, T= 0 °C , other (R,R)-1,2-bis(alkane- or -arenesulfonymamino)cyclohexanes, other temperatures, other dialkylzinc derivatives, other aldehydes, Product distribution Takahashi, Hideyo; Kawakita, Takashi; Ohno, Masaji; Yoshioka, Masato; Kobayashi, Susumu; Tetrahedron; vol. 48; nb. 27; (1992); p. 5691 - 5700 View in Reaxys With (1S,2S)-N-methyl-1-(2-pyridyl)-2-methylbutylamine, multistep reaction; other optically active 1-(2-pyridyl)alkylamines as chiral ligands, other temperatures and reaction times; temperature dependence on the enantioselectivity; ΔΔG(excit.), ΔΔH(excit.), ΔΔS(excit.), Product distribution, Thermodynamic data, Mechanism Conti; Falorni; Giacomelli; Soccolini; Tetrahedron; vol. 48; nb. 41; (1992); p. 8993 - 9000 View in Reaxys With titanium(IV) isopropylate, chiral TADDOL-titanates in toluene, T= -25 °C , different chiral TADDOL-derived titanates; high enantioselectivity (-> (S)-1-phenylpropan-1-ol); absence and excess of (i-PrO)4Ti; other aldehydes, Mechanism, Product distribution Seebach, Dieter; Plattner, Dietmar A.; Beck, Albert K.; Wang, Yan Ming; Hunziker, Daniel; Petter, Walter; Helvetica Chimica Acta; vol. 75; nb. 7; (1992); p. 2171 - 2209 View in Reaxys With (-)-1-piperidino-3,3-dimethyl-2-butanol in hexane, Time= 12h, T= -10 °C , further tertiary η-aminoalcohols with various ees; asymmetric amplifying in enantioselectivity, Product distribution Oguni, N.; Matsuda, Y.; Kaneko, T.; Journal of the American Chemical Society; vol. 110; nb. 23; (1988); p. 7877 - 7878 View in Reaxys With (1R,3R,5R)-3-(diphenylhydroxymethyl)-2-azabicyclo<3.3.0>octane in toluene, Time= 48h, Ambient temperature, other aldehydes and chiral reagents; var. temperatures and reagent concentrations, Product distribution Wallbaum, Sabine; Martens, Juergen; Tetrahedron: Asymmetry; vol. 4; nb. 4; (1993); p. 637 - 640 View in Reaxys in diethyl ether, hexane, Time= 25h, T= -10 °C , var. temp., var. time, absence or presence var. chiral pyridine ligands, other aldehyde, Product distribution

22/258

2018-07-03 17:29:03

Falorni, Massimo; Giacomelli, Giampaolo; Gazzetta Chimica Italiana; vol. 122; nb. 8; (1992); p. 339 - 340 View in Reaxys With (S)-η-hydroxy N-methylsulfoximine derived from cyclodecanone in hexane, T= 0 °C , other aldehydes, var. (S)-η-hydroxy sulfoximines; enantioselectivity of alkylation, Product distribution Bolm, Carsten; Mueller, Juergen; Schlingloff, Gunther; Zehnder, Margareta; Neuburger, Markus; Journal of the Chemical Society, Chemical Communications; nb. 2; (1993); p. 182 - 183 View in Reaxys With 1-[η(R)-(N,N-dimethylamino)ethyl]-2-(η'-hydroxypropyl)benzene * Cr(CO)2P(OPh)3 in toluene, Time= 18h, T= 0 °C , enantioselective addition of diethylzinc to other aldehydes; other chiral (arene)chromium complexes Uemura, Motokazu; Miyake, Ryuta; Nakayama, Kazuo; Shiro, Motoo; Hayashi, Yuji; Journal of Organic Chemistry; vol. 58; nb. 5; (1993); p. 1238 - 1244 View in Reaxys With PhCH(OH)CH(C2H5)N(CH3)CH(C2H5)CH[OSi(CH3)2t-Bu]Ph in hexane, toluene, Time= 24h, Ambient temperature, other chiral diethanolamines and their lithium alcoholates; var. time, Product distribution, Mechanism De Vries; Brussee; Kruse; Van Der Gen; Tetrahedron Asymmetry; vol. 4; nb. 9; (1993); p. 1987 - 1990 View in Reaxys With (R)-(+)-3-hydroxypyrrolidine lithium salt in toluene, Time= 40h, Ambient temperature, other chiral ligands derived from L-hydroxyproline and its lithium alkoxides; other aromatic aldehydes Mehler; Martens; Wallbaum; Synthetic Communications; vol. 23; nb. 19; (1993); p. 2691 - 2699 View in Reaxys With (2R,5S)-2-hydroxymethyl-1,4-diaza<4.3.0>bicyclononane in dichloromethane, Time= 16h, T= -15 °C , var. optically active 2-hydroxymethyl piperazines and their lithium salts, solvents, temp., and reaction times, Product distribution Falorni, Massimo; Satta, Michele; Conti, Sandra; Giacomelli, Giampaolo; Tetrahedron: Asymmetry; vol. 4; nb. 11; (1993); p. 2389 - 2398 View in Reaxys With lithium (S)-<(1R,3R,5R)-2-benzyl-2-azabicyclo<3.3.0>octan-3-yl>(2,4,6-trimethylphenyl)methanolate in hexane, toluene, Time= 16h, T= 22 °C , further chiral η-amino alcohols, effect on enantioselectivity, Product distribution Stingl, Klaus; Martens, Juergen; Liebigs Annalen der Chemie; nb. 5; (1994); p. 491 - 496 View in Reaxys With (1S,2R)-2-<N-<4-(benzyloxy)butyl>-N-butylamino>-1-phenylpropan-1-ol, multistep reaction: 1) hexane, 0 deg C, 10 min; 2) hexane, 0 deg C, 48 h; further reagents; enantioselectivity Watanabe, Masami; Soai, Kenso; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); nb. 7; (1994); p. 837 - 842 View in Reaxys With lithium (R)-1,1-diphenyl-3-(isopropylthio)-2-propylamino-1-propanoxide, multistep reaction; other sulfur-containing ηamino alcohols and their lithium salts as catalysts for the enantioselective addition Mehler, Thomas; Martens, Juergen; Tetrahedron: Asymmetry; vol. 5; nb. 2; (1994); p. 207 - 210 View in Reaxys With (-)-(1S)-1-hydroxymethyl-2-dimethylaminomethylferrocene in toluene, Time= 3h, Ambient temperature, var. time, enantiomer excess of 1-hydroxymethyl-2-dimethylaminomethylferrocene, and benzaldehyde/ferrocene derivative ratio; other aldehydes, Product distribution Nicolosi, Giovanni; Patti, Angela; Morrone, Raffaele; Piattelli, Mario; Tetrahedron: Asymmetry; vol. 5; nb. 9; (1994); p. 1639 - 1642 View in Reaxys With titanium(IV) isopropylate, (2R,3R)-η,η,η',η'-tetraphenylbicyclo<2.2.2>octane-2,3-dimethanol in hexane, Time= 120h, T= -78 °C , various chiral bicyclic diols investigated; enantiomer ratio determined by GC, Product distribution

23/258

2018-07-03 17:29:03

Waldmann, Herbert; Weigerding, Michael; Dreisbach, Claus; Wandrey, Christian; Helvetica Chimica Acta; vol. 77; nb. 8; (1994); p. 2111 - 2116 View in Reaxys With 1,2-isopropylidene-5-deoxy-5-pyrrolidinoo-η-D-xylofuranose in toluene, Time= 10h, Ambient temperature, other 1,2-isopropylidene-5-deoxy-5-dialkylamino-η-D-xylofuranoses, Product distribution Cho; Kim; Synthetic Communications; vol. 25; nb. 2; (1995); p. 167 - 175 View in Reaxys With (3'S,1''S)-2-(3'-isopropyl)oxazolyl-6-(1''-hydroxy-2,2-dimethyl)propylpyridine in hexane, toluene, Time= 24h, T= -78 °C , other aromatic aldehydes, var. ligands, temp., Product distribution Macedo, Emmanuel; Moberg, Christina; Tetrahedron: Asymmetry; vol. 6; nb. 2; (1995); p. 549 - 558 View in Reaxys With titanium(IV) isopropylate in toluene, Time= 5h, T= -30 °C , (1S,2R)-N-(O,O-dimethylthiophosphoryl)norephedrine and other chiral hydrogen phosphoramidates, hydrogen phosphinamides and their thio analogs as catalysts; without Ti(Oi-Pr)4; different solvents and temperatures, Product distribution Soai, Kenso; Ohno, Yoshiaki; Inoue, Yukikazu; Tsuruoka, Toshihiro; Hirose, Yuji; Recueil des Travaux Chimiques des Pays-Bas; vol. 114; nb. 4-5; (1995); p. 145 - 152 View in Reaxys With (1R,5R,8S)-(+)-7-Allyl-2-benzyl-8-isopropyl-3-oxa-2,7-diazabicyclo<3.3.0>octan in hexane, Time= 12h, T= -25 °C , different 3-oxa-2,7-diazabicyclo<3.3.0>octanes and reaction temperature, Product distribution Aurich, Hans Guenter; Gentes, Christian; Harms, Klaus; Tetrahedron; vol. 51; nb. 38; (1995); p. 10497 - 10512 View in Reaxys With poly(1-<<2-(hydroxydiphenylmethyl)pyrrolidin-1-yl>ethoxycarbonyl>-1,3-dimethyl-3-(octadecyloxycarbonyl)tetramethylene) in hexane, Time= 0.5h, enantioselectivity, various aldehydes, Product distribution, Rate constant Dreisbach, Claus; Wischnewski, Gisela; Kragl, Ugo; Wandrey, Christian; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); nb. 7; (1995); p. 875 - 878 View in Reaxys With 3endo-dimethylamino-bornan-2exo-ol, multistep reaction; enantioselective addition promoted by var. diastetereomers of (dimethylamino)borneol Kitamura, Masato; Suga, Seiji; Niwa, Makoto; Noyori, Ryoji; Journal of the American Chemical Society; vol. 117; nb. 17; (1995); p. 4832 - 4842 View in Reaxys in toluene, Time= 15h, Ambient temperature, various chiral diselenide catalysts, temp., solv., Product distribution Wirth, Thomas; Tetrahedron Letters; vol. 36; nb. 43; (1995); p. 7849 - 7852 View in Reaxys With chiral diazole ligand <(+)-camphorpyrazole and (R)-(+)-styrene oxide adduct> in hexane, toluene, Ambient temperature, other chiral ligands; var. reaction time, Product distribution Kotsuki, Hiyoshizo; Hayakawa, Hiroyuki; Wakao, Masahiro; Shimanouchi, Tomoyasu; Ochi, Masamitsu; Tetrahedron: Asymmetry; vol. 6; nb. 11; (1995); p. 2665 - 2668 View in Reaxys With (S)-diphenylprolinol in toluene, Time= 48h, T= 0 °C , different catalysts, Product distribution Liu, Guangcheng; Ellman, Jonathan A.; Journal of Organic Chemistry; vol. 60; nb. 24; (1995); p. 7712 - 7713 View in Reaxys With n-butyllithium, (R)-3-<Me2N(phenyl)methyl>pentan-3-ol in hexane, toluene, T= 20 °C , var. of catalyst, temp., Product distribution Peper, Viola; Martens, Juergen; Chemische Berichte; vol. 129; nb. 6; (1996); p. 691 - 695 View in Reaxys

24/258

2018-07-03 17:29:03

With (1R,2S)-exo-3-(phenylsulfanyl)-1,7,7-trimethylbicyclo<2.2.1>heptan-2-ol in hexane, Time= 13.5h, T= -78 - 20 °C , var. solvents, reaction times and isoborneol derived sulfides, Product distribution, Mechanism Arai; Nagata; Masaki; Chemical and Pharmaceutical Bulletin; vol. 43; nb. 12; (1995); p. 2243 - 2245 View in Reaxys With (+)-(S,1S)-1-(2-pyridinium)-1-indanolene tricarbonylchromium in toluene, Ambient temperature, var. chiral arene chromium complexes or without complexation, Product distribution Malfait; Pelinski; Brocard; Tetrahedron Asymmetry; vol. 7; nb. 3; (1996); p. 653 - 656 View in Reaxys With (R)-2-phenyl-5,6,7,8-tetrahydro-6,6-dimethyl-5,7-methano-8-quinolinol in hexane, toluene, Time= 3h, T= 24 °C , other chiral ligands, var. temp. times, Product distribution Collomb, Phillippe; Zelewsky, Alex von; Tetrahedron: Asymmetry; vol. 6; nb. 12; (1995); p. 2903 - 2904 View in Reaxys With (1S,3a'R,6a'R)-<1-benzyl-2-(hexahydro-cyclopenta<b>pyrrole-1'-yl)-ethyl>-methyl-amine in toluene, T= 110 °C , other chiral 1,2-diamines, chiral η-amino alcohols and its Li-salts; var. temp.; enantioselective asymmetric addition, Product distribution Eilers; Wilken; Martens; Tetrahedron Asymmetry; vol. 7; nb. 8; (1996); p. 2343 - 2357 View in Reaxys With titanium(IV) isopropylate, chiral phosphoramidate derived from η-amino alcohol in toluene, T= -20 °C , multistep; other chiral ligands, also without Ti(OiPr)4; product/yield distribution Hulst, Ron; Heres, Hero; Fitzpatrick, Kevin; Peper, Nathalie C.M.W.; Kellogg, Richard M.; Tetrahedron Asymmetry; vol. 7; nb. 9; (1996); p. 2755 - 2760 View in Reaxys With (R)-2,2-dimethyl-1,3-thiazolidine-η,η-diphenylmethanol in toluene, Ambient temperature, other 2,2-disubstituted-1,3-thiazolidine-η,η-diphenyl-methanols; other aldehydes, Product distribution Huang, Hsiang-Ling; Lin, Ya-Chuan; Chen, Shyh-Fong; Wang, Chia-Lin J.; Liu, Lee Tai; Tetrahedron Asymmetry; vol. 7; nb. 11; (1996); p. 3067 - 3070 View in Reaxys With 5-Deoxy-1,2-O-isopropylidene-5-morpholino-η-D-xylofuranose in toluene, Time= 10h, T= 25 °C , various temp., time and 1,2-O-isopropylidene-5-deoxy-5-N,N-dialkyl (or -N-monoalkyl)amino-η-D-xylofuranose derivatives as catalysts; also further aldehydes, Product distribution Cho, Byung Tae; Kim, Namdu; Journal of the Chemical Society - Perkin Transactions 1; nb. 24; (1996); p. 2901 - 2907 View in Reaxys With (1R,3S)-1-(2,2-dimethyl-1-propyl)-3-(3-hydroxy-3-pentyl)-1,2,3,4-tetrahydro-η-carboline in toluene, Time= 46h, Ambient temperature, further aldehyde; further chiral 1,2,3,4-tetrahydro-η-carbolines, Product distribution Dai, Wei-Min; Zhu, Hua Jie; Hao, Xiao-Jiang; Tetrahedron Letters; vol. 37; nb. 33; (1996); p. 5971 - 5974 View in Reaxys With (R,R)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine in toluene, Time= 24h, Ambient temperature, effect of the solvent, the reaction temp. and time, Product distribution, Mechanism Cozzi, Pier Giorgio; Papa, Angelo; Umani-Ronchi, Achille; Tetrahedron Letters; vol. 37; nb. 26; (1996); p. 4613 - 4616 View in Reaxys With titanium(IV) isopropylate, (1S,4S,5R)-N-tosyl-4-hydroxy-2,6-diazabicyclo<3.3.0>octane in hexane, toluene, Time= 15h, T= -78 °C , steroselective addition, further catalyst Lin, Guo-Qiang; Shi, Zhi-Cai; Tetrahedron; vol. 53; nb. 4; (1997); p. 1369 - 1382 View in Reaxys With diethylzinc, (R)-N,N,N',N'-tetra-isopropyl-2,2'-dihydroxy-1,1'-binaphthyl-3,3'-dicarboxamide in tetrahydrofuran, hexane, Time= 15h, T= 0 °C , other reagents, Product distribution

25/258

2018-07-03 17:29:03

Kitajima, Hiroshi; Ito, Katsuji; Aoki, Yuko; Katsuki, Tsutomu; Bulletin of the Chemical Society of Japan; vol. 70; nb. 1; (1997); p. 207 - 217 View in Reaxys With (S)-2-amino-3-butyl-1-<4-(4-methoxyphenyl)-phenyl>heptan-3-ol in toluene, Time= 31h, T= 0 °C , var. inductors, var. temp., other aldehydes, Product distribution Beliczey, Juliane; Giffels, Guido; Kragl, Udo; Wandrey, Christian; Tetrahedron Asymmetry; vol. 8; nb. 10; (1997); p. 1529 1530 View in Reaxys With (1S,2R)-2-(cis-2,6-dimethylpiperidino)-1-indanol in toluene, Time= 20h, Ambient temperature, enantioselective addition, other chiral ligands, other aldehydes, Product distribution Sola, Lluis; Vidal-Ferran, Anton; Moyano, Albert; Perica, Miquel A.; Riera, Antoni; Tetrahedron Asymmetry; vol. 8; nb. 10; (1997); p. 1559 - 1568 View in Reaxys With (1R,2R)-2-endo-hydroxy-2-exo-(N,N-dimethylamino-2-phenyl)-1,3,3-trimethylbicyclo<2.2.1>heptane in hexane, toluene, Time= 24h, Ambient temperature, var. optically active aminoalcohols, Product distribution Genov, Miroslav; Kostova, Kalina; Dimitrov, Vladimir; Tetrahedron Asymmetry; vol. 8; nb. 11; (1997); p. 1869 - 1876 View in Reaxys With (1R,3S,4S)-2-methyl-2-azabicyclo<2.2.1>heptane-3-exo-diphenylmethanol in hexane, toluene, Time= 7h, Ambient temperature, var. chiral ligands; other aldehydes, Product distribution Nakano, Hiroto; Kumagai, Noriyuki; Matsuzaki, Hisao; Kabuto, Chizuko; Hongo, Hiroshi; Tetrahedron Asymmetry; vol. 8; nb. 9; (1997); p. 1391 - 1401 View in Reaxys With chiral polymeric polybinaphthol catalyst in toluene, Time= 12h, T= 0 °C , other reagent, reaction time, temperature, Product distribution Huang; Hu; Zheng; Anderson; Pu; Journal of the American Chemical Society; vol. 119; nb. 18; (1997); p. 4313 - 4314 View in Reaxys With (ηR,ηR)-(1-methyl-octahydro-cyclopenta<b>pyrrol-2-yl)-1'-(4-methyl-phenyl)-methanol in toluene, T= 21 °C , other amino alcohols; enantioselectivity, Product distribution Wilken, Joerg; Groeger, Harald; Kossenjans, Michael; Martens, Juergen; Tetrahedron Asymmetry; vol. 8; nb. 16; (1997); p. 2761 - 2771 View in Reaxys With (1R,2R)-1-phenyl-1-(piperidin-1-yl)-3-(trityloxy)propan-2-ol in toluene, Time= 3h, Ambient temperature, other reagents, solvent, temperatures, durations; the effect of reagent amounts on the conversion and enantioselectivity, Product distribution Vidal-Ferran, Anton; Moyano, Albert; Pericas, Miquel A.; Riera, Antoni; Journal of Organic Chemistry; vol. 62; nb. 15; (1997); p. 4970 - 4982 View in Reaxys With titanium(IV) isopropylate, 4 A molecular sieve, N,N'-[[(phenylmethyl)imino]bis[(1S)-1-(1-methylethyl)-2,1-ethanediyl]]bis[1,1,1-trifluoro]methanesulfonamide in toluene, Time= 102h, T= -78 - -30 °C , other homochiral bis(ethylsulfonamide)amines, Product distribution Cernerud, Magnus; Skrinning, Anna; Bergere, Isabelle; Moberg, Christina; Tetrahedron Asymmetry; vol. 8; nb. 20; (1997); p. 3437 - 3441 View in Reaxys With titanium(IV) isopropylate, (S)-[1,1']-binaphthalenyl-2,2'-diol, ammonium chloride, Time= 1h, T= 0 °C , enantioselectivity; var. ald. educts; var. temperatures, Product distribution, Mechanism Mori, Maki; Nakai, Takeshi; Tetrahedron Letters; vol. 38; nb. 35; (1997); p. 6233 - 6236 View in Reaxys With (S)-N-methyl-N-phenyl-2-amino-3-methylbutan-1-thiol in toluene, Ambient temperature, other aldehydes and reagents, Product distribution

26/258

2018-07-03 17:29:03

Anderson, James C.; Harding, Michael; Chemical Communications; nb. 3; (1998); p. 393 - 394 View in Reaxys in hexane, toluene, Time= 15h, T= 0 °C , various ferrocene compounds as a catalysts, Product distribution Fukuzawa, Shin-Ichi; Kato, Hirohisa; Synlett; nb. 7; (1998); p. 727 - 728 View in Reaxys With (1R,2R,6S,8S,9R)-8-methyl-9-methylamino-7-oxabicyclo<4.3.0>nonan-2-ol, other reagents, Product distribution Aurich, Hans Guenter; Geiger, Michael; Gentes, Christian; Harms, Klaus; Koester, Heiner; Tetrahedron; vol. 54; nb. 13; (1998); p. 3181 - 3196 View in Reaxys With (5S,7S,8R)-5,7-methane-6,6,-dimethyl-8-(dimethylhydroxymethyl0-2-phenyl-5,6,7,8-tetrahydroqunoline in hexane, toluene, Time= 1.5h, Ambient temperature, var. diastereom. pure hydroxy and thiol derivs. of (5S,7S)-5,7-methane-6,6-dimethyl-2phenyl-5,6,7,8-tetrahydroquinoline Chelucci, Giorgio; Berta, Daniela; Fabbri, Davide; Pinna, Gerard A.; Saba, Antonio; Ulgheri, Fausta; Tetrahedron Asymmetry; vol. 9; nb. 11; (1998); p. 1933 - 1940 View in Reaxys With titanium(IV) isopropylate, n-butyllithium, (4S,5S)-2-tert-butyl-6-<(2,2-dimethyl-4-phenyl-<1,3>dioxan-5-ylimino)methyl>phenol in hexane, toluene, Time= 24h, T= -35 °C , various ligands, additives and time; further aldehydes, Product distribution Mino, Takashi; Oishi, Katsuhiko; Yamashita, Masakazu; Synlett; nb. 9; (1998); p. 965 - 966 View in Reaxys With (1S,3R,4R)-3-(hydroxymethyl)-2-methyl-2-azabicyclo<2.2.1>heptane in hexane, toluene, Time= 24h, T= 0 °C , other reagents: other 2-azanorbornylmethanols, other reaction temperature and time, Product distribution, Mechanism Guijarro, David; Pinho, Pedro; Andersson, Pher G.; Journal of Organic Chemistry; vol. 63; nb. 8; (1998); p. 2530 - 2535 View in Reaxys With C7H7NC2H2C(C2H5)2OH in hexane, toluene, Time= 60h, T= -23 °C , other reagent, temperatrure, reaction time, Product distribution Tanner, David; Korno, Hanne T.; Guijarro, David; Andersson, Pher G.; Tetrahedron; vol. 54; nb. 47; (1998); p. 14213 14232 View in Reaxys With (2R,3R)-3-(cis-2,6-dimethylpiperidino)-3-phenyl-1,2-propanediol-resin in toluene, Time= 24h, Ambient temperature, enantioselectivity, various resins, Product distribution Vidal-Ferran, Anton; Bampos, Nick; Moyano, Albert; Pericas, Miquel A.; Riera, Antoni; Sanders, Jeremy K.M.; Journal of Organic Chemistry; vol. 63; nb. 18; (1998); p. 6309 - 6318 View in Reaxys With (S)-N-methyl-N-phenyl-1-amino-3-methylbutan-1-thiol in hexane, toluene, Time= 8h, Ambient temperature, other aldehydes, var. chiral thiols and time, Product distribution Anderson, James C.; Cubbon, Rachel; Harding, Michael; James, Daniel S.; Tetrahedron Asymmetry; vol. 9; nb. 19; (1998); p. 3461 - 3490 View in Reaxys With (-)-ephedrine-mesoporous micelle templated silica in hexane, toluene, T= 0 °C , enantioselective alkylation, Mechanism Lasperas; Bellocq; Brunel; Moreau; Tetrahedron Asymmetry; vol. 9; nb. 17; (1998); p. 3053 - 3064 View in Reaxys With (1'S,2''S,5'R,8'S)-8,8-bi<2'-(1'',1''-diphenyl-1''-hydroxypropan-2''-yl)-3',7'-dioxa-2'-azabicyclo<3.3.0>octane in hexane, Time= 24h, T= 0 °C , various ligands, Product distribution Baskaran, Subramanian; Aurich, Hans Guenter; Biesemeier, Frank; Harms, Klaus; Journal of the Chemical Society - Perkin Transactions 1; nb. 22; (1998); p. 3717 - 3724

27/258

2018-07-03 17:29:03

View in Reaxys With titanium(IV) isopropylate, 2-tert-butyl-6-<(2-hydroxy-1,1,2-triphenylethylimino)methyl>-4-methoxyphenol in toluene, Time= 12h, T= -20 - 10 °C , various temp., time, further imines, Product distribution Fleischer, Ralf; Braun, Manfred; Synlett; nb. 12; (1998); p. 1441 - 1443 View in Reaxys With (1S,2R)-N-benzyl-N-methyl-ephedrinium bromide in hexane, acetonitrile, Time= 168h, Yield given. Title compound not separated from byproducts Soai, Kenso; Watanabe, Masami; Journal of the Chemical Society, Chemical Communications; nb. l; (1990); p. 43 - 44 View in Reaxys With (1R,2S)-N-isopropyl-N-methylnorephedrine, Ambient temperature, Yield given. Yields of byproduct given Chaloner, Penny A.; Langadianou, Eugenia; Tetrahedron Letters; vol. 31; nb. 36; (1990); p. 5185 - 5188 View in Reaxys With (S)-2-amino-4-methylpentan-1-ol in toluene, Time= 43h, T= 20 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Oguni, Nobuki; Omi, Takao; Tetrahedron Letters; vol. 25; nb. 26; (1984); p. 2823 - 2824 View in Reaxys 72 % Chromat.

With CH3CH<N(CH3)(CH(CH3)2)>CH2OHC6H5 in hexane, Time= 48h, T= 25 °C Chaloner, Penny A.; Perera, Renuka S. A.; Tetrahedron Letters; vol. 28; nb. 26; (1987); p. 3013 - 3014 View in Reaxys With bornane bidentate ligand in hexane, T= 0 °C , Yield given. Yields of byproduct given Oppolzer, Wolfgang; Radinov, Rumen N.; Tetrahedron Letters; vol. 29; nb. 44; (1988); p. 5645 - 5648 View in Reaxys With lithium salt of 2-dimethylhydroxymethyl-1-(2-pyridylmethyl)pyrrolidine in hexane, T= 0 °C Chelucci, Giorgio; Falorni, Massimo; Giacomelli, Giampaolo; Tetrahedron: Asymmetry; vol. 1; nb. 11; (1990); p. 843 - 849 View in Reaxys in hexane, toluene, Time= 69h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Rosini, Carlo; Franzini, Livia; Pini, Dario; Salvadori, P.; Tetrahedron: Asymmetry; vol. 1; nb. 9; (1990); p. 587 - 588 View in Reaxys With (1S,2R)-N-C6H5CH2O(CH2)4-N-methylnorephedrine in hexane, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Soai, Kenso; Watanabe, Masami; Tetrahedron: Asymmetry; vol. 2; nb. 2; (1991); p. 97 - 100 View in Reaxys With dilithium salt of (2S,5S)-2, 5-diisopropylpiperazine, 1) toluene, hexane, RT, 30 min, 2) RT, 20h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Niwa, Seiji; Soai, Kenso; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); (1991); p. 2717 - 2720 View in Reaxys With (1R,2S)-N-isopropyl-N-methylnorephedrine in toluene, Time= 48h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Chaloner, Penny A.; Langadianou, Eugenia; Perera, S. A. Renuka; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); (1991); p. 2731 - 2735 View in Reaxys With chiral arene chromium complex 2 in toluene, Time= 18h, T= 0 °C , Yield given. Yields of byproduct given

28/258

2018-07-03 17:29:03

Uemura, Motokazu; Miyake, Ryuta; Shiro, Motoo; Hayashi, Yuji; Tetrahedron Letters; vol. 32; nb. 35; (1991); p. 4569 4572 View in Reaxys With dilithium salt of (2S,5S)-2, 5-diisopropylpiperazine in hexane, toluene, Time= 20h, Ambient temperature, Yield given Soai, Kenso; Niwa, Seiji; Yamada, Yasuyuki; Inoue, Hideo; Tetrahedron Letters; vol. 28; nb. 41; (1987); p. 4841 - 4842 View in Reaxys With (2R,3R)-4-dimethylamino-3-methyl-1,2-diphenyl-butan-2-ol in toluene, Time= 16h, Ambient temperature, Yield given. Yields of byproduct given Muchow, G.; Vannoorenberghe, Y.; Buono, G.; Tetrahedron Letters; vol. 28; nb. 49; (1987); p. 6163 - 6166 View in Reaxys With polymer-bound (1R,2S)-(-)-ephedrine in hexane, Time= 48h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Soai, Kenso; Niwa, Seiji; Watanabe, Masami; Journal of Organic Chemistry; vol. 53; nb. 4; (1988); p. 927 - 928 View in Reaxys With polymer-bound chiral amino alcohol in toluene, Time= 62h, T= 0 °C , Yield given. Title compound not separated from byproducts Itsuno, Shinichi; Frechet, Jean M.J.; Journal of Organic Chemistry; vol. 52; nb. 18; (1987); p. 4140 - 4142 View in Reaxys With Quinine in toluene, Yield given. Yields of byproduct given. Title compound not separated from byproducts Smaardijk, Ab. A.; Wynberg, Hans; Journal of Organic Chemistry; vol. 52; nb. 1; (1987); p. 135 - 137 View in Reaxys With 1.) ligand 1, 1.) Et2O, hexane, RT, 20 min, 2.) Et2O, hexane, -10 deg C, 25 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Falorni, Massimo; Giacomelli, Giampaolo; Gazzetta Chimica Italiana; vol. 122; nb. 8; (1992); p. 339 - 340 View in Reaxys With (R)-2,2-dimethyl-1-(pyridin-2-yl)propan-1-ol, 1.) ether, hexane, RT, 20 min, 2.) ether, hexane, 20 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Chelucci, Giorgio; Soccolini, Franco; Tetrahedron: Asymmetry; vol. 3; nb. 10; (1992); p. 1235 - 1238 View in Reaxys With pyrrolidine in hexane, temp.: 0 deg C to r.t., Yield given. Title compound not separated from byproducts Masaki; Oda; Kazuta; Usui; Itoh; Xu; Tetrahedron Letters; vol. 33; nb. 35; (1992); p. 5089 - 5092 View in Reaxys With (1S,2R)-N-triflyl-1,2-(9,10-dihydro-9,10,anthraceno)-2-aminoethanol in toluene, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Kimura; Sugiyama; Ishizuka; Kunieda; Tetrahedron Letters; vol. 33; nb. 22; (1992); p. 3147 - 3150 View in Reaxys With titanium(IV) isopropylate, C,C,C-trifluoro-N-(2-trifluoromethanesulfonylaminocyclohexyl)methanesulfonamide in hexane, toluene, Time= 2h, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Takahashi, Hideyo; Kawakita, Takashi; Ohno, Masaji; Yoshioka, Masato; Kobayashi, Susumu; Tetrahedron; vol. 48; nb. 27; (1992); p. 5691 - 5700 View in Reaxys With titanium(IV) isopropylate, chiral "TADDOL-derived titanate" in toluene, Time= 15h, T= -22 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Seebach, Dieter; Plattner, Dietmar A.; Beck, Albert K.; Wang, Yan Ming; Hunziker, Daniel; Petter, Walter; Helvetica Chimica Acta; vol. 75; nb. 7; (1992); p. 2171 - 2209

29/258

2018-07-03 17:29:03

View in Reaxys With PhCH(OH)CH(C2H5)N(CH3)CH(C2H5)CH[OSi(CH3)2t-Bu]Ph in hexane, toluene, Time= 24h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts De Vries; Brussee; Kruse; Van Der Gen; Tetrahedron Asymmetry; vol. 4; nb. 9; (1993); p. 1987 - 1990 View in Reaxys With chiral <(CH3)2NCH(CH3)CH(Ph)S>2 in toluene, Time= 20h, Ambient temperature, Yield given. Title compound not separated from byproducts Hof; Poelert; Peper; Kellogg; Tetrahedron Asymmetry; vol. 5; nb. 1; (1994); p. 31 - 34 View in Reaxys With (+)-(1R,2S)-bis<N-ethyl-N-(2-hydroxy-2-phenyl-1-methyl)-ethyl>-m-xylyenediamine in hexane, toluene, Time= 20h, T= 20 °C , Yield given. Yields of byproduct given Andres, Jose M.; Martinez, Maria A.; Pedrosa, Rafael; Perez-Encabo, Alfonso; Tetrahedron: Asymmetry; vol. 5; nb. 1; (1994); p. 67 - 72 View in Reaxys With lithium (S)-<(1R,3R,5R)-2-benzyl-2-azabicyclo<3.3.0>octan-3-yl>(phenyl)methanolate in hexane, toluene, Time= 16h, T= 22 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Stingl, Klaus; Martens, Juergen; Liebigs Annalen der Chemie; nb. 5; (1994); p. 491 - 496 View in Reaxys With (1R,2S)-1-phenyl-2-(N-methyl-N-benzylamino)propan-1-ol, 1) hexane, 10 min, 0 deg C; 2) hexane, 0 deg C, 45 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Watanabe, Masami; Soai, Kenso; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); nb. 7; (1994); p. 837 - 842 View in Reaxys With (R)-(+)-2-<2',2'-dimethyl-1'-(2''-pyridyl)propoxy>-1,1-di-(η-naphthyl)ethanol in hexane, toluene, Time= 1.16667h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Ishizaki; Fujita; Shimamoto; Hoshino; Tetrahedron Asymmetry; vol. 5; nb. 3; (1994); p. 411 - 424 View in Reaxys With (-)-(1S)-1-hydroxymethyl-2-dimethylaminomethylferrocene in toluene, Time= 3h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Nicolosi, Giovanni; Patti, Angela; Morrone, Raffaele; Piattelli, Mario; Tetrahedron: Asymmetry; vol. 5; nb. 9; (1994); p. 1639 - 1642 View in Reaxys With (3'S,1''S)-2-(3'-phenyl)oxazolyl-6-(1''-hydroxy-2,2-dimethyl)propylpyridine in hexane, toluene, Time= 24h, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Macedo, Emmanuel; Moberg, Christina; Tetrahedron: Asymmetry; vol. 6; nb. 2; (1995); p. 549 - 558 View in Reaxys With (1R)-2-N<(R)-1-phenylethyl>amino-1-phenylethanol in hexane, toluene, Time= 6h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Iuliano; Pini; Salvadori; Tetrahedron Asymmetry; vol. 6; nb. 3; (1995); p. 739 - 744 View in Reaxys With (R,S)-1-<1-(N,N-dimethylaminoethyl)-2-<(2'-hydroxycyclohexylseleno)>ferrocene, 1.) toluene, hexane, 0 deg C, 10 min, 2.) toluene, hexane, RT, 15 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Fukuzawa; Tsudzuki; Tetrahedron Asymmetry; vol. 6; nb. 5; (1995); p. 1039 - 1042 View in Reaxys

30/258

2018-07-03 17:29:03

With N-(2',2'-diphenylethyl-2'-hydroxyethyl)-(2R,5R)-bis(methoxymethyl)pyrrolidine, 1.) hexane, 0 deg C, 0.5 h, 2.) hexane, 0 deg C, 24 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Shi, Min; Satoh, Yukihiro; Makihara, Takechi; Masaki, Yukio; Tetrahedron: Asymmetry; vol. 6; nb. 9; (1995); p. 2109 2112 View in Reaxys With chiral diazole ligand <(+)-camphorpyrazole and (R)-(+)-styrene oxide adduct> in hexane, toluene, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Kotsuki, Hiyoshizo; Hayakawa, Hiroyuki; Wakao, Masahiro; Shimanouchi, Tomoyasu; Ochi, Masamitsu; Tetrahedron: Asymmetry; vol. 6; nb. 11; (1995); p. 2665 - 2668 View in Reaxys With (+)-(S,1S)-1-(2-pyridinium)-1-indanolene tricarbonylchromium in toluene, Ambient temperature, Yield given. Title compound not separated from byproducts Malfait; Pelinski; Brocard; Tetrahedron Asymmetry; vol. 7; nb. 3; (1996); p. 653 - 656 View in Reaxys With (R)-2-phenyl-5,6,7,8-tetrahydro-6,6-dimethyl-5,7-methano-8-quinolinol in hexane, toluene, Time= 3h, T= 24 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Collomb, Phillippe; Zelewsky, Alex von; Tetrahedron: Asymmetry; vol. 6; nb. 12; (1995); p. 2903 - 2904 View in Reaxys With (S,S)-2,7-diethyl-1,6-bis(10'-hydroxy-9'-phenanthryl)pyrocoll in dichloromethane, Time= 22h, T= -20 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Furusho, Yoshio; Tsunoda, Akihiro; Aida, Takuzo; Journal of the Chemical Society - Perkin Transactions 1; nb. 2; (1996); p. 183 - 190 View in Reaxys With <((S)-1-methylpyrrolidin-2-yl)-CH2S->2, 1.) hexane, toluene, r.t., 2 h, 2.) 0 deg C, 48 h, Yield given. Yields of byproduct given. Title compound not separated from byproducts Gibson, Colin L.; Chemical Communications; nb. 5; (1996); p. 645 - 646 View in Reaxys With (+)-(S,1S)-<2-(N,N-dimethylaminomethyl)ferrocenyl>-1-propanol in toluene, Time= 4h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Maciejewski, Lucien A.; Goetgheluck, Sophie J.; Delacroix, Olivier A.; Brocard, Jacques S.; Tetrahedron Asymmetry; vol. 7; nb. 6; (1996); p. 1573 - 1576 View in Reaxys With (S,S)-(-)-1,2-diphenylethanediol zinc dialkoxide in toluene, Time= 18h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Prasad; Joshi; Tetrahedron Asymmetry; vol. 7; nb. 7; (1996); p. 1957 - 1960 View in Reaxys With 5-Deoxy-1,2-O-isopropylidene-5-morpholino-η-D-xylofuranose in toluene, 1.) 25 deg C, 30 min, 2.) 25 deg C, 10 h, Yield given. Yields of byproduct given. Title compound not separated from byproducts Cho, Byung Tae; Kim, Namdu; Journal of the Chemical Society - Perkin Transactions 1; nb. 24; (1996); p. 2901 - 2907 View in Reaxys With (1'R,5'S,8'S)-(+)-1-(8'-methyl-3',7'-dioxa-2'-azabicyclo<3.3.0>oct-2'-yl)cyclohexanemethanol in hexane, 1.) 0 deg C, 10 min, 2.) -55 deg C, 121 h, Yield given. Yields of byproduct given. Title compound not separated from byproducts Aurich, Hans Guenter; Biesemeier, Frank; Geiger, Michael; Harms, Klaus; Liebigs Annales; nb. 2; (1997); p. 423 - 434 View in Reaxys With (1R,3S)-1-(2,2-dimethyl-1-propyl)-3-(3-hydroxy-3-pentyl)-1,2,3,4-tetrahydro-η-carboline in toluene, Time= 46h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts

31/258

2018-07-03 17:29:03

Dai, Wei-Min; Zhu, Hua Jie; Hao, Xiao-Jiang; Tetrahedron Letters; vol. 37; nb. 33; (1996); p. 5971 - 5974 View in Reaxys With scalemic η-amino disulfide in toluene, Time= 22h, T= 0 °C , Yield given. Yields of byproduct given Fulton, David A.; Gibson, Colin L.; Tetrahedron Letters; vol. 38; nb. 11; (1997); p. 2019 - 2022 View in Reaxys With (R)-(+)-(t-Bu)2C6H2OH-NC5H3CH3 in toluene, Time= 48h, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Zhang, Huichang; Xue, Feng; Mak; Chan, Kin Shing; Journal of Organic Chemistry; vol. 61; nb. 23; (1996); p. 8002 - 8003 View in Reaxys With (1R,2S)-(-)-1-phenyl-2-piperidinopropane-1-thiol in toluene, Time= 12h, T= 0 °C , Yield given. Yields of byproduct given Kang, Jahyo; Kim, Jin Bum; Kim, Jeong Whan; Lee, Duckhwan; Journal of the Chemical Society. Perkin Transactions 2; nb. 2; (1997); p. 189 - 194 View in Reaxys With (S)-2-N,N-dibutylamino-3-butyl-1-<4-(4-methoxyphenyl)-phenyl>heptan-3-ol in toluene, Time= 10h, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Beliczey, Juliane; Giffels, Guido; Kragl, Udo; Wandrey, Christian; Tetrahedron Asymmetry; vol. 8; nb. 10; (1997); p. 1529 1530 View in Reaxys With N-ethyl (3S)-3-diphenylhydroxymethyl-2-azabicyclo<2.2.2>octane in hexane, toluene, Time= 7h, Ambient temperature, Yield given. Yields of byproduct given Nakano, Hiroto; Iwasa, Kazuto; Hongo, Hiroshi; Heterocycles; vol. 44; nb. 1; (1997); p. 435 - 442 View in Reaxys With 1,3-bis<N-<(1S,2R)-2-hydroxy-1-methyl-2-phenylethyl>-N-methylaminomethyl>benzene in hexane, toluene, Time= 48h, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Williams, David R.; Fromhold, Mark G.; Synlett; nb. SPEC. ISS.; (1997); p. 523 - 524 View in Reaxys With (5S,7S,8S)-8-amino-5,6,7,8-tetrahydro-6,6-dimethyl-2-phenyl-5,7-methanoquinoline in hexane, toluene, Time= 30h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Chelucci, Giorgio; Pinna, Gerard A.; Saba, Antonio; Tetrahedron Asymmetry; vol. 8; nb. 15; (1997); p. 2571 - 2578 View in Reaxys With ferrocenyl oxazoline derivative in toluene, Time= 6h, T= 0 °C , Yield given Bolm, Carsten; Muniz Fernandez, Kilian; Seger, Andreas; Raabe, Gerhard; Synlett; vol. 1997; nb. 9; (1997); p. 1051 1052 View in Reaxys With N,N,N-tris<((3S)-isopropyl-2-oxazolin-2-yl)methyl>amine in toluene, Time= 48h, T= 0 °C , Yield given. Title compound not separated from byproducts Chan; Zheng; Canadian Journal of Chemistry; vol. 75; nb. 6; (1997); p. 629 - 633 View in Reaxys With (1R,2S,3S,5R)-2-(benzylmethylamino)-6,6-dimethylbicyclo<3.1.1>heptan-3-ol, 1.) toluene, 25 deg C, 15 min, 2.) toluene, 0 deg C, 12 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Goralski, Christian T.; Chrisman, William; Hasha, Dennis L.; Nicholson, Lawrence W.; Rudolf, Philip R.; Zakett, Donald; Singaram, Bakthan; Tetrahedron Asymmetry; vol. 8; nb. 23; (1997); p. 3863 - 3871 View in Reaxys With (S)-N-methyl-N-phenyl-2-amino-3-methylbutan-1-thiol in toluene, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts

32/258

2018-07-03 17:29:03

Anderson, James C.; Harding, Michael; Chemical Communications; nb. 3; (1998); p. 393 - 394 View in Reaxys With (3S)-3-mercaptomethyl-2-<(R)-1-phenylethyl>-2-azabicyclo<2.2.2>octane in hexane, toluene, Time= 7h, T= 0 °C , Yield given. Yields of byproduct given Nakano, Hiroto; Iwasa, Kazuto; Hongo, Hiroshi; Heterocycles; vol. 46; nb. 1; (1997); p. 267 - 274 View in Reaxys With 3-deoxy-3-N,N-di-n-octylamino-1,2;5,6-di-O-isopropylidene-D-altritol in toluene, Time= 12h, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Cho, Byung Tae; Chun, Yu Sung; Tetrahedron Asymmetry; vol. 9; nb. 9; (1998); p. 1489 - 1492 View in Reaxys With (S,R)-2-(1-dimethylaminoethyl)ferrocenecarbaldehyde in hexane, toluene, 1.) 0 deg C, 30 min, 2. ) 0 deg C, 15 h, Yield given. Yields of byproduct given. Title compound not separated from byproducts Fukuzawa, Shin-Ichi; Kato, Hirohisa; Synlett; nb. 7; (1998); p. 727 - 728 View in Reaxys With chiral o-hydroxyphenyl diazaphospholidine oxide in tetrahydrofuran, Time= 48h, T= 20 °C , Yield given. Yields of byproduct given Brunel, Jean-Michel; Constantieux, Thierry; Legrand, Olivier; Buono, Gerard; Tetrahedron Letters; vol. 39; nb. 19; (1998); p. 2961 - 2964 View in Reaxys With (5S,7S,8R)-5,7-methane-6,6-dimethyl-8-(dimethylhydroxymethyl)-2-phenyl-5,6,7,8-tetrahydroquinoline in hexane, toluene, Time= 1.5h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Chelucci, Giorgio; Berta, Daniela; Fabbri, Davide; Pinna, Gerard A.; Saba, Antonio; Ulgheri, Fausta; Tetrahedron Asymmetry; vol. 9; nb. 11; (1998); p. 1933 - 1940 View in Reaxys With N-(2-hydroxy-2,2-diphenylethyl)-2,5-bis(methoxymethyl)pyrrolidine, 1.) hexane, 0 deg C, 0.5 h, 2.) hexane, 0 deg C, 24 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Shi, Min; Satoh, Yukihiro; Masaki, Yukio; Journal of the Chemical Society - Perkin Transactions 1; nb. 16; (1998); p. 2547 2552 View in Reaxys With titanium(IV) isopropylate, trans-(1S,2S)-bis<(S)-BocNHCH(PhCH2)CH2SO2NH>cyclohexane in toluene, T= -78 - -20 °C , Title compound not separated from byproducts Gennari, Cesare; Ceccarelli, Simona; Piarulli, Umberto; Montalbetti, Christian A. G. N.; Jackson, Richard F. W.; Journal of Organic Chemistry; vol. 63; nb. 16; (1998); p. 5312 - 5313 View in Reaxys With (S)-N-methyl-N-phenyl-2-amino-3-methylbutan-1-thiol in hexane, toluene, Time= 8h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Anderson, James C.; Cubbon, Rachel; Harding, Michael; James, Daniel S.; Tetrahedron Asymmetry; vol. 9; nb. 19; (1998); p. 3461 - 3490 View in Reaxys With (+)-(1R)-1-<o-(N,N-dimethylaminomethyl)phenyl>indanol in toluene, Time= 16h, T= 20 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Malfait, Stephane; Pelinski, Lydie; Brocard, Jacques; Tetrahedron Asymmetry; vol. 9; nb. 15; (1998); p. 2595 - 2610 View in Reaxys With chiral ligand (6) in hexane, toluene, Time= 1h, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Collomb, Philippe; Von Zelewsky, Alex; Tetrahedron Asymmetry; vol. 9; nb. 21; (1998); p. 3911 - 3917

33/258

2018-07-03 17:29:03

View in Reaxys With (1S,2R)-N-benzyl-N-methylephedrinium chloride in hexane, Time= 72h, Yield given. Title compound not separated from byproducts Soai, Kenso; Watanabe, Masami; Journal of the Chemical Society, Chemical Communications; nb. l; (1990); p. 43 - 44 View in Reaxys With polymeric chiral amino alkohol 12 in hexane, toluene, Time= 6h, T= 0 °C , Yield given. Title compound not separated from byproducts Itsuno, Shinichi; Sakurai, Yoshiki; Ito, Koichi; Maruyama, Toshihiro; Nakahama, Seiichi; Frechet, J. M. J.; Journal of Organic Chemistry; vol. 55; nb. 1; (1990); p. 304 - 310 View in Reaxys With bornane tridentate ligand in hexane, T= 0 °C , Yield given. Yields of byproduct given Oppolzer, Wolfgang; Radinov, Rumen N.; Tetrahedron Letters; vol. 29; nb. 44; (1988); p. 5645 - 5648 View in Reaxys With (2R,5S)-2-(diphenylhydroxymethyl)-3-phenyl-1,3-diazabicyclo<3.3.0>octane in hexane, cyclohexane, Time= 15h, Ambient temperature, Yield given. Yields of byproduct given Asami, Masatoshi; Inoue, Seiichi; Chemistry Letters; nb. 4; (1991); p. 685 - 688 View in Reaxys With (1S,2R)-(-)-2-(N,N-di-n-butylamino)-1-phenylpropan-1-ol, 1.) hexane, rt, 20 min 2.) hexane, 0 deg C, 16 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Soai, Kenso; Yokoyama, Shuji; Hayasaka, Tomoiki; Journal of Organic Chemistry; vol. 56; nb. 13; (1991); p. 4264 - 4268 View in Reaxys With titanium(IV) isopropylate in toluene, Yield given. Yields of byproduct given Schmidt, Beat; Seebach, Dieter; Angewandte Chemie; vol. 103; nb. 1; (1991); p. 100 - 101 View in Reaxys With homoannularly bridged hydroxyamino ferrocene in toluene, Time= 12h, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Wally, Hans; Widhalm, Michael; Weissensteiner, Walter; Schoegl, Karl; Tetrahedron: Asymmetry; vol. 4; nb. 3; (1993); p. 285 - 288 View in Reaxys With (S)-η-hydroxy N-methylsulfoximine derived from cyclodecanone in hexane, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Bolm, Carsten; Mueller, Juergen; Schlingloff, Gunther; Zehnder, Margareta; Neuburger, Markus; Journal of the Chemical Society, Chemical Communications; nb. 2; (1993); p. 182 - 183 View in Reaxys With 1-[η(R)-(N,N-dimethylamino)ethyl]-2-(η'-hydroxypropyl)benzene * Cr(CO)2P(OPh)3 in toluene, Time= 18h, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Uemura, Motokazu; Miyake, Ryuta; Nakayama, Kazuo; Shiro, Motoo; Hayashi, Yuji; Journal of Organic Chemistry; vol. 58; nb. 5; (1993); p. 1238 - 1244 View in Reaxys With (1R,3S)-1,2,2-trimethyl-1,3-cyclopentanediamine derivative in hexane, toluene, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Urabe, Hirokazu; Yamakawa, Tetsuro; Sato, Fumie; Tetrahedron: Asymmetry; vol. 3; nb. 1; (1992); p. 5 - 8 View in Reaxys With (1S,2R)-N,N-dimethyl-1,2-(9,10-dihydro-9,10,anthraceno)-2-aminoethanol in toluene, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts

34/258

2018-07-03 17:29:03

Kimura; Sugiyama; Ishizuka; Kunieda; Tetrahedron Letters; vol. 33; nb. 22; (1992); p. 3147 - 3150 View in Reaxys With titanium(IV) isopropylate, N,N’-(1R,2R)-cyclohexane-1,2-diylbis(1,1,1-trifluoromethanesulfonamide) in hexane, toluene, Time= 2h, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Takahashi, Hideyo; Kawakita, Takashi; Ohno, Masaji; Yoshioka, Masato; Kobayashi, Susumu; Tetrahedron; vol. 48; nb. 27; (1992); p. 5691 - 5700 View in Reaxys With (2R,5S)-2-hydroxymethyl-1,4-diaza<4.3.0>bicycloionane in dichloromethane, Time= 16h, T= -15 °C , Title compound not separated from byproducts Falorni, Massimo; Satta, Michele; Conti, Sandra; Giacomelli, Giampaolo; Tetrahedron: Asymmetry; vol. 4; nb. 11; (1993); p. 2389 - 2398 View in Reaxys With titanium(IV) isopropylate, (4R,5R)-2,2-dimethyl-η,η,η',η'-tetra(p-N,N-dimethylaminophenyl)-1,3-dioxolane-4,5-dimethanol in toluene, Time= 20h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Brunner, Henri; Zang, Er-Le; Zeitschrift fuer Naturforschung, B: Chemical Sciences; vol. 48; nb. 12; (1993); p. 1723 - 1726 View in Reaxys With lithium (S)-<(1R,3R,5R)-2-benzyl-2-azabicyclo<3.3.0>octan-3-yl>(2,4,6-trimethylphenyl)methanolate in hexane, toluene, Time= 16h, T= 22 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Stingl, Klaus; Martens, Juergen; Liebigs Annalen der Chemie; nb. 5; (1994); p. 491 - 496 View in Reaxys With lithium (R)-1,1-diphenyl-3-(isopropylthio)-2-propylamino-1-propanoxide, 1.) toluene, from -20 deg C to RT, 2.) toluene, RT, 16 h, Multistep reaction. Title compound not separated from byproducts Mehler, Thomas; Martens, Juergen; Tetrahedron: Asymmetry; vol. 5; nb. 2; (1994); p. 207 - 210 View in Reaxys With chiral secondary amino alcohol catalyst in toluene, Ambient temperature, Yield given. Yields of byproduct given Tanaka, Kazuhiko; Ushio, Hideki; Suzuki, Hitomi; Journal of the Chemical Society, Chemical Communications; nb. 22; (1989); p. 1700 - 1701 View in Reaxys With (S)-(-)-2-<2',2'-dimethyl-1'-(2''-pyridyl)propoxy>-1,1-di-(η-naphthyl)ethanol in hexane, toluene, Time= 1.16667h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Ishizaki; Fujita; Shimamoto; Hoshino; Tetrahedron Asymmetry; vol. 5; nb. 3; (1994); p. 411 - 424 View in Reaxys With (+)-(1R)-1-hydroxymethyl-2-dimethylaminomethylferrocene in toluene, Time= 3h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Nicolosi, Giovanni; Patti, Angela; Morrone, Raffaele; Piattelli, Mario; Tetrahedron: Asymmetry; vol. 5; nb. 9; (1994); p. 1639 - 1642 View in Reaxys With titanium(IV) isopropylate, (2R,3R)-η,η,η',η'-tetraphenylbicyclo<2.2.2>octane-2,3-dimethanol in hexane, Time= 120h, T= -78 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Waldmann, Herbert; Weigerding, Michael; Dreisbach, Claus; Wandrey, Christian; Helvetica Chimica Acta; vol. 77; nb. 8; (1994); p. 2111 - 2116 View in Reaxys With (3'S,1''S)-2-(3'-isopropyl)oxazolyl-6-(1''-hydroxy-2,2-dimethyl)propylpyridine in hexane, toluene, Time= 24h, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Macedo, Emmanuel; Moberg, Christina; Tetrahedron: Asymmetry; vol. 6; nb. 2; (1995); p. 549 - 558 View in Reaxys

35/258

2018-07-03 17:29:03

With (1R,5R,8S)-(+)-7-Allyl-2-benzyl-8-isopropyl-3-oxa-2,7-diazabicyclo<3.3.0>octan in hexane, Time= 12h, T= -25 °C , Title compound not separated from byproducts Aurich, Hans Guenter; Gentes, Christian; Harms, Klaus; Tetrahedron; vol. 51; nb. 38; (1995); p. 10497 - 10512 View in Reaxys With poly(1-<<2-(hydroxydiphenylmethyl)pyrrolidin-1-yl>ethoxycarbonyl>-1,3-dimethyl-3-(octadecyloxycarbonyl)tetramethylene in hexane, Yield given. Yields of byproduct given. Title compound not separated from byproducts Dreisbach, Claus; Wischnewski, Gisela; Kragl, Ugo; Wandrey, Christian; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); nb. 7; (1995); p. 875 - 878 View in Reaxys With (1R,3S,4S)-2-methyl-2-azabicyclo<2.2.1>heptane-3-exo-diphenylmethanol, 1.) toluene, hexane, 0 deg C, 30 min, 2.) toluene, hexane, 0 deg C, 7 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Nakano; Kumagai; Kabuto; Matsuzaki; Hongo; Tetrahedron Asymmetry; vol. 6; nb. 6; (1995); p. 1233 - 1236 View in Reaxys With (S,R)-1-<1-(N,N-dimethylaminoethyl)-2-<(2'-hydroxycyclohexylseleno)>ferrocene, 1.) toluene, hexane, 0 deg C, 10 min, 2.) toluene, hexane, RT, 15 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Fukuzawa; Tsudzuki; Tetrahedron Asymmetry; vol. 6; nb. 5; (1995); p. 1039 - 1042 View in Reaxys With chiral diazole ligand <(+)-camphorpyrazole and (S)-(-)-styrene oxide adduct> in hexane, toluene, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Kotsuki, Hiyoshizo; Hayakawa, Hiroyuki; Wakao, Masahiro; Shimanouchi, Tomoyasu; Ochi, Masamitsu; Tetrahedron: Asymmetry; vol. 6; nb. 11; (1995); p. 2665 - 2668 View in Reaxys With (S)-diphenyl(1-methylpyrrolidin-2-yl)methanol in toluene, Time= 48h, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Liu, Guangcheng; Ellman, Jonathan A.; Journal of Organic Chemistry; vol. 60; nb. 24; (1995); p. 7712 - 7713 View in Reaxys With n-butyllithium, (R)-3-<Me2N(phenyl)methyl>pentan-3-ol in hexane, toluene, T= 20 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Peper, Viola; Martens, Juergen; Chemische Berichte; vol. 129; nb. 6; (1996); p. 691 - 695 View in Reaxys With (S,S)-(-)-1,4-Dipyrrolidino-2,3-butandiol, 1) toluene, room temperature, 30 min, 2) room temperature, 24 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Cho, Byung Tae; Kim, Namdu; Synthetic Communications; vol. 26; nb. 12; (1996); p. 2273 - 2280 View in Reaxys With (1R,2S)-exo-3-(phenylsulfanyl)-1,7,7-trimethylbicyclo<2.2.1>heptan-2-ol, 1.) hexane, 0 deg C, 0.5 h, 2.) hexane, from -78 deg C to RT, 13 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Arai; Nagata; Masaki; Chemical and Pharmaceutical Bulletin; vol. 43; nb. 12; (1995); p. 2243 - 2245 View in Reaxys With (R,R)-1,6-bis(2'-hydroxy-1'-naphthyl)-2,7-dimethylpyrocoll in toluene, Time= 44h, T= -20 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Furusho, Yoshio; Tsunoda, Akihiro; Aida, Takuzo; Journal of the Chemical Society - Perkin Transactions 1; nb. 2; (1996); p. 183 - 190 View in Reaxys With (S)-diphenylprolinol in hexane, T= 0 °C , Title compound not separated from byproducts

36/258

2018-07-03 17:29:03

Kragl, Udo; Dreisbach, Claus; Angewandte Chemie; vol. 108; nb. 6; (1996); p. 684 - 685 View in Reaxys With (R)-1,1-dimethyl-1,3-thiazolidine-η,η-diphenylmethanol in toluene, Time= 120h, T= 4 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Huang, Hsiang-Ling; Lin, Ya-Chuan; Chen, Shyh-Fong; Wang, Chia-Lin J.; Liu, Lee Tai; Tetrahedron Asymmetry; vol. 7; nb. 11; (1996); p. 3067 - 3070 View in Reaxys With (1S,2R,1'S,5'R,8'R)-(-)-2-(8'-methyl-3',7'-dioxa-2'-azabicyclo<3.3.0>oct-2'-yl)-1-phenylpropan-1-ol in toluene, 1.) 0 deg C, 10 min, 2.) 0 deg C, 20 h, Yield given. Yields of byproduct given. Title compound not separated from byproducts Aurich, Hans Guenter; Biesemeier, Frank; Geiger, Michael; Harms, Klaus; Liebigs Annales; nb. 2; (1997); p. 423 - 434 View in Reaxys With (R,R)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine in toluene, -40 degC, 1 h, room t., 24 h, Yield given. Yields of byproduct given. Title compound not separated from byproducts Cozzi, Pier Giorgio; Papa, Angelo; Umani-Ronchi, Achille; Tetrahedron Letters; vol. 37; nb. 26; (1996); p. 4613 - 4616 View in Reaxys With (1S,2R)-1-phenyl-2-piperidinopropane-1-thiol in toluene, Time= 12h, T= 0 °C , Yield given. Yields of byproduct given Kang, Jahyo; Kim, Jin Bum; Kim, Jeong Whan; Lee, Duckhwan; Journal of the Chemical Society. Perkin Transactions 2; nb. 2; (1997); p. 189 - 194 View in Reaxys With (S)-2,2'-dihydroxy-1,1'-binaphthyl, titanium(IV) isopropylate in hexane, dichloromethane, Time= 5h, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Zhang, Fu-Yao; Yip, Chiu-Wing; Cao, Rong; Chan, Albert S. C.; Tetrahedron Asymmetry; vol. 8; nb. 4; (1997); p. 585 - 589 View in Reaxys With (S)-2-amino-3-butyl-1-<4-(4-methoxyphenyl)-phenyl>heptan-3-ol in toluene, Time= 31h, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Beliczey, Juliane; Giffels, Guido; Kragl, Udo; Wandrey, Christian; Tetrahedron Asymmetry; vol. 8; nb. 10; (1997); p. 1529 1530 View in Reaxys With (1S,2R)-2-(cis-2,6-dimethyl-1-piperidino)-1-indanol in hexane, toluene, Time= 20h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Sola, Lluis; Vidal-Ferran, Anton; Moyano, Albert; Perica, Miquel A.; Riera, Antoni; Tetrahedron Asymmetry; vol. 8; nb. 10; (1997); p. 1559 - 1568 View in Reaxys With (1R,3S,4S)-2-methyl-2-azabicyclo<2.2.1>heptane-3-exo-diphenylmethanol in hexane, toluene, Time= 7h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Nakano, Hiroto; Kumagai, Noriyuki; Matsuzaki, Hisao; Kabuto, Chizuko; Hongo, Hiroshi; Tetrahedron Asymmetry; vol. 8; nb. 9; (1997); p. 1391 - 1401 View in Reaxys With 2,6-bis<N-<(1S,2R)-2-hydroxy-1-methyl-2-phenylethyl>-N-methylaminomethyl>pyridine in hexane, toluene, Time= 48h, T= -70 - -50 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Williams, David R.; Fromhold, Mark G.; Synlett; nb. SPEC. ISS.; (1997); p. 523 - 524 View in Reaxys With (3S,4aR,7aR)-1-methylbicyclo<4.3.0>-1-azanonan-3-ol, 1.) toluene, -40 deg C, 30 min, 2.) toluene, 24 deg C, 40 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Wilken, Joerg; Kossenjans, Michael; Groeger, Harald; Martens, Juergen; Tetrahedron Asymmetry; vol. 8; nb. 12; (1997); p. 2007 - 2015 View in Reaxys

37/258

2018-07-03 17:29:03

With titanium(IV) isopropylate, calcium hydride, (1S,2R,4S)-N-benzyl-2-hydroxy-7,7-dimethylbicyclo<2.2.1>hept-1-ylmethanesulfonamide in toluene, Time= 1h, T= 20 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Ramoen, Diego J.; Yus, Miguel; Tetrahedron Asymmetry; vol. 8; nb. 14; (1997); p. 2479 - 2496 View in Reaxys With (1R,2R)-1-phenyl-1-(piperidin-1-yl)-3-(trityloxy)propan-2-ol, 1) toluene, room temperature, 20 min, 2) toluene, hexanes, room temperature, 3 h, Multistep reaction. Title compound not separated from byproducts Vidal-Ferran, Anton; Moyano, Albert; Pericas, Miquel A.; Riera, Antoni; Journal of Organic Chemistry; vol. 62; nb. 15; (1997); p. 4970 - 4982 View in Reaxys With (1S,2S,5R)-1-N,N-dimethylaminopropyl-2-isopropyl-5-methylcyclohexan-1-ol in hexane, toluene, Time= 18h, Yield given. Yields of byproduct given. Title compound not separated from byproducts Genov, Miroslav; Dimitrov, Vladimir; Ivanova, Valentina; Tetrahedron Asymmetry; vol. 8; nb. 22; (1997); p. 3703 - 3706 View in Reaxys With titanium(IV) isopropylate, (S)-[1,1']-binaphthalenyl-2,2'-diol, ammonium chloride, 1.) toluene/hexane, 0 deg C, 1 h; 2.) toluene/hexane, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Mori, Maki; Nakai, Takeshi; Tetrahedron Letters; vol. 38; nb. 35; (1997); p. 6233 - 6236 View in Reaxys With (3R)-3-mercaptomethyl-2-<(R)-1-phenylethyl>-2-azabicyclo<2.2.2>octane in hexane, toluene, Time= 7h, T= 0 °C , Yield given. Yields of byproduct given Nakano, Hiroto; Iwasa, Kazuto; Hongo, Hiroshi; Heterocycles; vol. 46; nb. 1; (1997); p. 267 - 274 View in Reaxys With (2R,9R)-2,9-di-(monomethyl)-amino-1,1,10,10-tetraphenyl-4,7-dithia-decan-1,10-diol in toluene, Time= 24h, T= 23 °C , Yields of byproduct given. Title compound not separated from byproducts Kossenjans, Michael; Martens, Juergen; Tetrahedron Asymmetry; vol. 9; nb. 8; (1998); p. 1409 - 1417 View in Reaxys With (R,S)-2-(1-dimethylaminoethyl)ferrocenecarbaldehyde in hexane, toluene, 1.) 0 deg C, 30 min, 2. ) 0 deg C, 15 h, Yield given. Yields of byproduct given. Title compound not separated from byproducts Fukuzawa, Shin-Ichi; Kato, Hirohisa; Synlett; nb. 7; (1998); p. 727 - 728 View in Reaxys With titanium(IV) isopropylate, n-butyllithium, (4S,5S)-2-tert-butyl-6-<(2,2-dimethyl-4-phenyl-<1,3>dioxan-5-ylimino)methyl>phenol in hexane, toluene, 1.) -78 deg C, 1 h, 2.) -35 deg C, 24 h, Yield given. Yields of byproduct given. Title compound not separated from byproducts Mino, Takashi; Oishi, Katsuhiko; Yamashita, Masakazu; Synlett; nb. 9; (1998); p. 965 - 966 View in Reaxys With titanium(IV) isopropylate, (R,R)-1,2-cyclohexanedi(styrenesulfonamide) in hexane, toluene, Time= 24h, T= -70 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Halm; Kurth; Angewandte Chemie - International Edition in English; vol. 37; nb. 4; (1998); p. 510 - 512 View in Reaxys With (1S,3R,4R)-2-benzyl-3-(hydroxymethyl)-2-azabicyclo<2.2.1>heptane, 1.) toluene, hexane, 20 min, 2.) toluene, hexane, 0 deg C -> room temperature, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Guijarro, David; Pinho, Pedro; Andersson, Pher G.; Journal of Organic Chemistry; vol. 63; nb. 8; (1998); p. 2530 - 2535 View in Reaxys With (2R,3R)-3-(cis-2,6-dimethylpiperidino)-3-phenyl-1,2-propanediol-Barlos resin in toluene, Time= 24h, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts

38/258

2018-07-03 17:29:03

Vidal-Ferran, Anton; Bampos, Nick; Moyano, Albert; Pericas, Miquel A.; Riera, Antoni; Sanders, Jeremy K.M.; Journal of Organic Chemistry; vol. 63; nb. 18; (1998); p. 6309 - 6318 View in Reaxys With (S)-2-tert-butyldimethylsilyloxy-1,1-di(2-pyridyl)propan-1-ol, 1.) hexane, toluene, -15 deg C, 15 min, 2.) hexane, toluene, RT, 10 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Kotsuki, Hiyoshizo; Hayakawa, Hiroyuki; Tateishi, Hirotaka; Wakao, Masahiro; Shiro, Motoo; Tetrahedron Asymmetry; vol. 9; nb. 18; (1998); p. 3203 - 3212 View in Reaxys With (1S,2R)-2-<(12-Benzyloxy-dodecyl)-N-butyl-amino>-1-phenyl-propan-1-ol in hexane, 1.) 10 min, 2.) 70 deg C, 6 h, Yield given. Yields of byproduct given. Title compound not separated from byproducts Hailes, Helen C.; Madden, James; Synlett; nb. 1; (1999); p. 105 - 107 View in Reaxys With chiral polybinaphthyl in toluene, Time= 12h, T= 0 °C , Addition, Title compound not separated from byproducts Hu, Qiao-Sheng; Huang, Wei-Sheng; Vitharana, Dilrukshi; Zheng, Xiao-Fan; Pu, Lin; Journal of the American Chemical Society; vol. 119; nb. 51; (1997); p. 12454 - 12464 View in Reaxys With N-(9-deoxyquinine-9-yl)benzamide in hexane, toluene, Time= 0.00666667h, T= 20 °C , Addition, Title compound not separated from byproducts Brunner, H.; Buegler, J.; Bulletin des Societes Chimiques Belges; vol. 106; nb. 2; (1997); p. 77 - 84 View in Reaxys With (S)-2-(1-pyrrolidinylmethyl)pyrrolidine in hexane, cyclohexane, Time= 17h, T= 0 °C , Addition, Title compound not separated from byproducts Asami, Masatoshi; Inoue, Seiichi; Bulletin of the Chemical Society of Japan; vol. 70; nb. 7; (1997); p. 1687 - 1690 View in Reaxys With chiral polybinaphthyl in toluene, T= 0 °C , Addition, Title compound not separated from byproducts Hu, Qiao-Sheng; Huang, Wei-Sheng; Vitharana, Dilrukshi; Zheng, Xiao-Fan; Pu, Lin; Journal of the American Chemical Society; vol. 119; nb. 51; (1997); p. 12454 - 12464 View in Reaxys With <(M)-N,N'-bis<<3-ethoxy-2-(hydroxy-ηO)phenyl>methylidene>-6,6'-dimethyl<1,1'-biphenyl>-2,2'-dimethanaminato(2-)ηN,ηN'>cobalt in toluene, Ambient temperature, various reagents; solvents;, Rate constant, Product distribution Keller, Felix; Rippert, Andreas Johannes; Helvetica Chimica Acta; vol. 82; nb. 1; (1999); p. 125 - 137 View in Reaxys With n-butyllithium, (P,P)-C108H144N4O4 in tetrahydrofuran, hexane, Time= 24h, Ambient temperature, other reagent, Product distribution Okubo, Hitoshi; Yamaguchi, Masahiko; Kabuto, Chizuko; Journal of Organic Chemistry; vol. 63; nb. 25; (1998); p. 9500 9509 View in Reaxys With (2S)-(-)-3-(-)-exo-(dimethylamino)isoborneol, dimethyl zinc(II) in toluene, T= 40 °C , Rate constant Kitamura, Masato; Hiromasa, Oka; Noyori, Ryoji; Tetrahedron; vol. 55; nb. 12; (1999); p. 3605 - 3614 View in Reaxys With (S)-(-)-1-benzyl-2-(1-hydroxy-1-methylethyl)-pyrrolidine, multistep reaction; also 4-methoxybenzaldehyde; var. chiral pyrrolidine derivatives as catalysts; var. solv., temp. and time, Product distribution, Mechanism Yang, Xiaowu; Shen, Jianheng; Da, Chaoshan; Wang, Rui; Choi, Michael C. K.; Yang, Liwei; Wong, Kwok-Yin; Tetrahedron Asymmetry; vol. 10; nb. 1; (1999); p. 133 - 138 View in Reaxys

39/258

2018-07-03 17:29:03

With 3-ethyl-1-isopropylmercapto-2-morpholino-pentan-3-ol, Time= 48h, T= 22 °C , other η-amino alcohols, Product distribution Kossenjans, Michael; Pennemann, Helmut; Martens, Juergen; Juanes, Olga; Rodriguez-Ubis, Juan C.; Brunet, Ernesto; Tetrahedron Asymmetry; vol. 9; nb. 23; (1998); p. 4123 - 4125 View in Reaxys With (S)-2-(4-methylpiperazin-1-ylmethyl)indoline in hexane, cyclohexane, Time= 15h, T= 0 °C , other aldehydes, other (S)indolines, var. amount of indolines, var. solvents and temp., Product distribution Asami, Masatoshi; Watanabe, Hiroyasu; Honda, Kiyoshi; Inoue, Seiichi; Tetrahedron Asymmetry; vol. 9; nb. 23; (1998); p. 4165 - 4173 View in Reaxys With (1R,R)-(-)-1-trimethylsilyl-2-(N-methyl,N-hydroxyethyl)aminoethylferrocene in toluene, Time= 24h, T= 25 °C , other ferrocenyl aminoalcohols and amine; var. temp., Product distribution Patti, Angela; Nicolosi, Giovanni; Howell, James A. S.; Humphries, Kristina; Tetrahedron Asymmetry; vol. 9; nb. 24; (1998); p. 4381 - 4394 View in Reaxys With 2-azabicyclo<3.3.0>octane-2-CH(CH3)CH2SH in hexane, T= 0 °C , Yield given, Yields of byproduct given. Title compound not separated from byproducts Aurich, Hans Guenter; Soeberdt, Michael; Tetrahedron Letters; vol. 39; nb. 17; (1998); p. 2553 - 2554 View in Reaxys With n-butyllithium, (R)-2-(N,N-dimethylamino)-2'-hydroxy-1,1'-binaphthyl in hexane, toluene, Time= 36h, Ambient temperature, other reagents, Yield given, Yields of byproduct given. Title compound not separated from byproducts Vyskocil, Stepn; Jaracz, Stanislav; Smrcina, Martin; Sticha, Martin; Hanus, Vladimir; Miroslav Poldsek; Kocovsky, Pavel; Journal of Organic Chemistry; vol. 63; nb. 22; (1998); p. 7727 - 7737 View in Reaxys With (S)-(+)-2-(3-methyl-2-pyridyl)-3,5-di-tert-butylphenol in hexane, toluene, 1.) -78 deg C, 10 min, 2.) -4 deg C, 48 h, Yields of byproduct given. Title compound not separated from byproducts Zhang, Huichang; Chan, Kin Shing; Journal of the Chemical Society - Perkin Transactions 1; nb. 4; (1999); p. 381 - 382 View in Reaxys With 2-azabicyclo<3.3.0>octane-2-CH(Ph)C(Ph)2OH in hexane, T= 0 °C , Yield given, Yields of byproduct given. Title compound not separated from byproducts Aurich, Hans Guenter; Soeberdt, Michael; Tetrahedron Letters; vol. 39; nb. 17; (1998); p. 2553 - 2554 View in Reaxys With <(M)-N,N'-bis<<3-ethoxy-2-(hydroxy-ηO)phenyl>methylidene>-6,6'-dimethyl<1,1'-biphenyl>-2,2'-dimethanaminato(2-)ηN,ηN'>cobalt in toluene, Ambient temperature, Title compound not separated from byproducts Keller, Felix; Rippert, Andreas Johannes; Helvetica Chimica Acta; vol. 82; nb. 1; (1999); p. 125 - 137 View in Reaxys With chiral o-hydroxyarylphosphine oxide in tetrahydrofuran, hexane, Time= 48h, Ambient temperature Legrand, Olivier; Brunel, Jean-Michel; Buono, Gerard; Tetrahedron Letters; vol. 39; nb. 51; (1998); p. 9419 - 9422 View in Reaxys With n-butyllithium, (R)-(-)-2-<N-(2"-adamantyl)-N-methylamino>-2'-hydroxy-1,1'-binaphthyl in hexane, toluene, Time= 36h, Ambient temperature, other reagents, Yield given, Yields of byproduct given. Title compound not separated from byproducts Vyskocil, Stepn; Jaracz, Stanislav; Smrcina, Martin; Sticha, Martin; Hanus, Vladimir; Miroslav Poldsek; Kocovsky, Pavel; Journal of Organic Chemistry; vol. 63; nb. 22; (1998); p. 7727 - 7737 View in Reaxys With (S)-(-)-1-benzyl-2-(1-methoxy-1,1-diphenylmethyl)-pyrrolidine, 1.) hexane, 0 deg C, 0.5 h, 2.) hexane, from 0 deg C to RT, 12 h, Yield given, Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts

40/258

2018-07-03 17:29:03

Yang, Xiaowu; Shen, Jianheng; Da, Chaoshan; Wang, Rui; Choi, Michael C. K.; Yang, Liwei; Wong, Kwok-Yin; Tetrahedron Asymmetry; vol. 10; nb. 1; (1999); p. 133 - 138 View in Reaxys With (S)-2-(4-methylpiperazin-1-ylmethyl)indoline in hexane, cyclohexane, Time= 15h, T= 0 °C , Yield given, Yields of byproduct given. Title compound not separated from byproducts Asami, Masatoshi; Watanabe, Hiroyasu; Honda, Kiyoshi; Inoue, Seiichi; Tetrahedron Asymmetry; vol. 9; nb. 23; (1998); p. 4165 - 4173 View in Reaxys With titanium(IV) isopropylate, (1R,2R)-N,N'-bis<(1S,4R)-7,7-dimethyl-2-oxo-bicyclo<2.2.1>heptylmethanesulfonyl>-1,2-cyclohexyldiamine, 1.) THF, -78 deg C, 0.5 h, 2.) THF, 27 deg C, 10 h, Yield given, Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Hwang, Chyuan-Der; Uang, Biing-Jiun; Tetrahedron Asymmetry; vol. 9; nb. 22; (1998); p. 3979 - 3984 View in Reaxys With (S)-1,2,2-triphenyl-2-(1-pyrrolidinyl)ethanol in hexane, toluene, Time= 3h, T= 0 °C , other reagents, solvent, Product distribution Reddy, Katamreddy Subba; Sola, Lluis; Moyano, Albert; Pericas, Miquel A.; Riera, Antoni; Journal of Organic Chemistry; vol. 64; nb. 11; (1999); p. 3969 - 3974 View in Reaxys With (1R,2R,2'S)-2-endo-(1'-diethylamino-2'-hydroxyethyl)-1,7,7-trimethylbicyclo<2.2.1>heptane-2-ol in hexane, toluene, Time= 24h, Ambient temperature, other chiral aminodiol catalysts; other solvents; var. reaction times, Product distribution Philipova, Irena; Dimitrov, Vladimir; Simova, Svetlana; Tetrahedron Asymmetry; vol. 10; nb. 7; (1999); p. 1381 - 1391 View in Reaxys With n-butyllithium, (L)-BuOCH2NBu2C(OH)Ph2 in toluene, Ambient temperature, Yield given, Yields of byproduct given Sibi, Mukund P.; Chen, Jian-xie; Cook, Gregory R.; Tetrahedron Letters; vol. 40; nb. 17; (1999); p. 3301 - 3304 View in Reaxys With 2-<(1S)-phenyl-(<(1'R)-1'-phenylethyl>amino)methyl>phenol in toluene, Time= 12h, T= 20 °C , Yield given, Yields of byproduct given. Title compound not separated from byproducts Palmieri, Gianni; European Journal of Organic Chemistry; nb. 4; (1999); p. 805 - 811 View in Reaxys With (R)-C56H70O6, Title compound not separated from byproducts Huang, Wei-Sheng; Pu, Lin; Journal of Organic Chemistry; vol. 64; nb. 12; (1999); p. 4222 - 4223 View in Reaxys With (1R,2S,2'S)-2-endo-(1'-diethylamino-2'-hydroxy-2'-methylpropyl)-1,7,7-trimethylbicyclo<2.2.1>heptane-2-ol in hexane, toluene, Time= 72h, Ambient temperature, Yield given, Yields of byproduct given. Title compound not separated from byproducts Philipova, Irena; Dimitrov, Vladimir; Simova, Svetlana; Tetrahedron Asymmetry; vol. 10; nb. 7; (1999); p. 1381 - 1391 View in Reaxys With n-butyllithium, (L)-BuOCH2NHBuC(OH)Ph2 in toluene, Ambient temperature, Yield given, Yields of byproduct given Sibi, Mukund P.; Chen, Jian-xie; Cook, Gregory R.; Tetrahedron Letters; vol. 40; nb. 17; (1999); p. 3301 - 3304 View in Reaxys With 2-<(1R)-phenyl-(<(1'R)-1'-phenylethyl>amino)methyl>phenol in toluene, Time= 4h, T= 20 °C , Yield given, Yields of byproduct given. Title compound not separated from byproducts Palmieri, Gianni; European Journal of Organic Chemistry; nb. 4; (1999); p. 805 - 811 View in Reaxys With (1R,2S,3S,5R)-(+)-6,6-dimethyl-2-(N-butylanilino)-methylbicyclo<3.1.1>heptane-2,3-diol in hexane, Time= 16h, Ambient temperature, Yield given, Yields of byproduct given. Title compound not separated from byproducts

41/258

2018-07-03 17:29:03

Cherng, Yie-Jia; Fang, Jim-Min; Lu, Ta-Jung; Journal of Organic Chemistry; vol. 64; nb. 9; (1999); p. 3207 - 3212 View in Reaxys With (1R,2R,2'S)-2-endo-(1'-diethylamino-2'-hydroxyethyl)-1,7,7-trimethylbicyclo<2.2.1>heptane-2-ol in hexane, toluene, Time= 24h, Ambient temperature, Yield given, Yields of byproduct given. Title compound not separated from byproducts Philipova, Irena; Dimitrov, Vladimir; Simova, Svetlana; Tetrahedron Asymmetry; vol. 10; nb. 7; (1999); p. 1381 - 1391 View in Reaxys With (1'R,2'S)-2-<2-(1-hydroxy-1-phenyl)propylaminocarbonyl>pyridine in hexane, toluene, Time= 72h, Ambient temperature, various chiral pyridine, or pyridine N-oxide ligands, Product distribution Derdau, Volker; Laschat, Sabine; Hupe, Eike; Koenig, Wilfried A.; Dix, Ina; Jones, Peter G.; European Journal of Inorganic Chemistry; nb. 6; (1999); p. 1001 - 1007 View in Reaxys With 1,1'-disubstituted ferrocenyl amino alcohol (11) in toluene, Time= 43h, Ambient temperature, other 1,1'-disubstituted ferrocenyl chiral alcohols, Product distribution Bastin, Stephanie; Delebecque, Nathalie; Agbossou, Francine; Brocard, Jacques; Pelinski, Lydie; Tetrahedron Asymmetry; vol. 10; nb. 9; (1999); p. 1647 - 1651 View in Reaxys With optically active 2-azabicyclo[3.3.0]octane derived alcohol in toluene, Time= 12h, T= 0 °C , Addition, Product distribution, Further Variations: Reagents, Temperatures, various reaction time Kossenjans, Michael; Soeberdt, Michael; Wallbaum, Sabine; Harms, Klaus; Martens, Juergen; Aurich, Hans Guenter; Journal of the Chemical Society - Perkin Transactions 1; nb. 16; (1999); p. 2353 - 2365 View in Reaxys With titanium(IV) isopropylate in toluene, Time= 2h, T= -20 °C , Addition, Product distribution, Further Variations: Catalysts Sellner, Holger; Seebach, Dieter; Angewandte Chemie - International Edition; vol. 38; nb. 13-14; (1999); p. 1918 - 1920 View in Reaxys With titanium(IV) isopropylate, (Sa,S,S)-2,2'-bis(2,2,2-trifluoro-1-hydroxyethyl)biphenyl in hexane, toluene, T= -78 - -30 °C , Addition Omote, Masaaki; Kominato, Akane; Sugawara, Michi; Sato, Kazuyuki; Ando, Akira; Kumadaki, Itsumaro; Tetrahedron Letters; vol. 40; nb. 30; (1999); p. 5583 - 5585 View in Reaxys With (S)-2-N-p-toluenesulfonamido-1,2-diphenylethanol, 1) toluene, 0 deg C, 30 min; 2) toluene, 0 deg C, 9 h, Yield given, Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Cho, Byung Tae; Chun, Yu Sung; Synthetic Communications; vol. 29; nb. 3; (1999); p. 521 - 531 View in Reaxys With 1,1'-disubstituted ferrocenyl di-(S)-2-amino-1,1-diphenyl-1-propanol in toluene, Time= 43h, Ambient temperature, Yield given, Yields of byproduct given. Title compound not separated from byproducts Bastin, Stephanie; Delebecque, Nathalie; Agbossou, Francine; Brocard, Jacques; Pelinski, Lydie; Tetrahedron Asymmetry; vol. 10; nb. 9; (1999); p. 1647 - 1651 View in Reaxys With optically active azabicyclo[3.3.0]octane derived alcohol in toluene, Time= 12h, T= 0 °C , Addition, Title compound not separated from byproducts Kossenjans, Michael; Soeberdt, Michael; Wallbaum, Sabine; Harms, Klaus; Martens, Juergen; Aurich, Hans Guenter; Journal of the Chemical Society - Perkin Transactions 1; nb. 16; (1999); p. 2353 - 2365 View in Reaxys With (1'R,2'S)-2-<2-(1-hydroxy-1-phenyl)propylaminocarbonyl>pyridine in hexane, toluene, Time= 72h, Ambient temperature, Yield given, Yields of byproduct given. Title compound not separated from byproducts Derdau, Volker; Laschat, Sabine; Hupe, Eike; Koenig, Wilfried A.; Dix, Ina; Jones, Peter G.; European Journal of Inorganic Chemistry; nb. 6; (1999); p. 1001 - 1007

42/258

2018-07-03 17:29:03

View in Reaxys With titanium(IV) isopropylate, (Ra)-2,2'-bis[(R)-2,2,2-trifluoro-1-hydroxyethyl]biphenyl in hexane, toluene, T= -78 - -30 °C , Addition Omote, Masaaki; Kominato, Akane; Sugawara, Michi; Sato, Kazuyuki; Ando, Akira; Kumadaki, Itsumaro; Tetrahedron Letters; vol. 40; nb. 30; (1999); p. 5583 - 5585 View in Reaxys With (1S,2R)-(+)-1-phenyl-2-(1-pyrrolidinyl)-1-propanol in hexane, Time= 20h, T= 0 °C , Addition, Title compound not separated from byproducts Soai, Kenso; Konishi, Takashi; Shibata, Takanori; Heterocycles; vol. 51; nb. 6; (1999); p. 1421 - 1426 View in Reaxys With (R)-(-)-diphenyl-(N-methylpiperidin-3-yl)methanol in toluene, Time= 24h, T= 0 °C , Addition, Title compound not separated from byproducts Lee, So Ha; Im, Dai Sig; Cheong, Chan Seong; Chung, Bong Young; Heterocycles; vol. 51; nb. 8; (1999); p. 1913 - 1919 View in Reaxys With 1,1'-disubstituted ferrocenyl di-pseudoephedrine in toluene, Time= 43h, Ambient temperature, Yield given, Yields of byproduct given. Title compound not separated from byproducts Bastin, Stephanie; Delebecque, Nathalie; Agbossou, Francine; Brocard, Jacques; Pelinski, Lydie; Tetrahedron Asymmetry; vol. 10; nb. 9; (1999); p. 1647 - 1651 View in Reaxys With N-(2,2-diphenyl-2-hydroxyethyl)-(S,S)-2,4-bis(methoxymethyl)azetidine, 1.) hexane, 0 deg C, 0.5 h, 2.) hexane, 0 deg C, 24 h, Yield given, Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Shi, Min; Jiang, Jian-Kang; Tetrahedron Asymmetry; vol. 10; nb. 9; (1999); p. 1673 - 1679 View in Reaxys With (-)-(R)-1-(η-N-butylaminobenzyl)-2-naphthol in toluene, Time= 48h, T= 20 °C , Addition, Product distribution, Further Variations: Reagents, Solvents, Temperatures Cardellicchio, Cosimo; Ciccarella, Giuseppe; Naso, Francesco; Perna, Filippo; Tortorella, Paolo; Tetrahedron; vol. 55; nb. 51; (1999); p. 14685 - 14692 View in Reaxys With titanium(IV) isopropylate, polymer supported 3,3'-functionazized (S)-BINOL in dichloromethane, Time= 24h, T= 0 °C , asymmetric addition, Product distribution Yang, Xiao-Wu; Sheng, Jian-Heng; Da, Chao-Shan; Wang, Heng-Shan; Su, Wu; Wang, Rui; Chan, Albert S. C.; Journal of Organic Chemistry; vol. 65; nb. 2; (2000); p. 295 - 296 View in Reaxys With (R)-2-(1-hydroxy-2,2-dimethylethyl)-6-phenylpyridine, Condensation, Product distribution, Further Variations: Reagents Bolm, Carsten; Dinter, Christian L.; Seger, Andreas; Hoecker, Hartwig; Brozio, Joerg; Journal of Organic Chemistry; vol. 64; nb. 16; (1999); p. 5730 - 5731 View in Reaxys With (2S,4R)-4-benzyloxy-2-(C(OH)Ph2)-1-methylpyrrolidine, Time= 4h, T= 0 °C , Addition, Product distribution, Further Variations: Catalysts, Reagents, reaction time Bae, Sung Jin; Kim, Sang-Wook; Hyeon, Taeghwan; Kim, B. Moon; Chemical Communications; nb. 1; (2000); p. 31 - 32 View in Reaxys With (R)-2-(1-hydroxy-2,2-dimethylethyl)-6-phenylpyridine, Condensation, Title compound not separated from byproducts Bolm, Carsten; Dinter, Christian L.; Seger, Andreas; Hoecker, Hartwig; Brozio, Joerg; Journal of Organic Chemistry; vol. 64; nb. 16; (1999); p. 5730 - 5731 View in Reaxys

43/258

2018-07-03 17:29:03

With (R)-6,6-diethyl-7-hydroxy-2-phenyl-6,7-dihydro-5H-<1>pyridine in hexane, toluene, Time= 24h, T= 0 - 20 °C , Yield given, Yields of byproduct given Kang, Jahyo; Kim, Ha Young; Kim, Joong Hyup; Tetrahedron Asymmetry; vol. 10; nb. 13; (1999); p. 2523 - 2533 View in Reaxys With titanium(IV) isopropylate, diphenylphosphoramide of (1R,2R)-diaminocyclohexane in dichloromethane, Time= 48h, T= -50 - -20 °C , Alkylation, Title compound not separated from byproducts Shi, Min; Sui, Wen-Sheng; Tetrahedron Asymmetry; vol. 10; nb. 17; (1999); p. 3319 - 3325 View in Reaxys With phenyl)hexan-3-ol in hexane, toluene, Time= 4h, T= 20 °C , Addition, Title compound not separated from byproducts Malezieux, Bernard; Andres, Roman; Gruselle, Michel; Rager, Marie-Noelle; Thorimbert, Serge; Tetrahedron Asymmetry; vol. 10; nb. 17; (1999); p. 3253 - 3257 View in Reaxys With (S)-diphenyl(1-methylpyrrolidin-2-yl)methanol in toluene, Time= 24h, T= 20 °C , Addition, Product distribution, Further Variations: Catalysts, amount of catalyst; asymm. induction Hodge, Philip; Kell, Roger J.; Ma, Jianbiao; Morris, Hugh; Australian Journal of Chemistry; vol. 52; nb. 11; (1999); p. 1041 - 1046 View in Reaxys With (S,R)-(-)-1-(ferrocenylethyl)prolinol in hexane, toluene, Time= 3h, T= 20 °C , Addition, Product distribution, Further Variations: Reagents Gotov, Battsengel; Toma, Stefan; Solcaniova, Eva; Cvengros, Jan; Tetrahedron; vol. 56; nb. 4; (2000); p. 671 - 675 View in Reaxys With titanium(IV) isopropylate, (R,R)-Argogel-NHCO(CH2)2CONC4H6(NHSO2(CH2)2NHBoc)2 in hexane, toluene, Time= 16h, T= -20 °C , Addition, Product distribution, Further Variations: Reagents Brouwer, Arwin J.; van Der Linden, Heiko J.; Liskamp, Rob M. J.; Journal of Organic Chemistry; vol. 65; nb. 6; (2000); p. 1750 - 1757 View in Reaxys With 1,3,5-triMe-1,3,5-tris[(4S)-4-iPr-1,3-oxazolin-2-yl]c-hexane in toluene, Time= 16h, T= 25 °C , Substitution, Product distribution, Further Variations: Reagents Chuang, Tsung-Hsun; Fang, Jim-Min; Bolm, Carsten; Synthetic Communications; vol. 30; nb. 9; (2000); p. 1627 - 1641 View in Reaxys With chiral 2,2'-bipyridine ligand in toluene, Time= 0.5h, T= 22 °C , Addition, Product distribution, Further Variations: Reagents, Solvents, Temperatures Kwong, Hoi-Lun; Lee, Wing-Sze; Tetrahedron Asymmetry; vol. 10; nb. 19; (1999); p. 3791 - 3801 View in Reaxys With chiral ferrocenyl aminoalcohol in toluene, Alkylation, Product distribution, Further Variations: Reagents Delacroix, Olivier; Picart-Goetgheluck, Sophie; Maciejewski, Lucien; Brocard, Jacques; Tetrahedron Asymmetry; vol. 10; nb. 22; (1999); p. 4417 - 4425 View in Reaxys With titanium(IV) isopropylate, (R,R)-TADDOL in toluene, Time= 2h, T= -20 °C , Addition, Product distribution, Further Variations: Reagents Rheiner, P. Beat; Seebach, Dieter; Chemistry - A European Journal; vol. 5; nb. 11; (1999); p. 3221 - 3236 View in Reaxys With C2-symmetric chiral oxazolinyl binaphthyl ligand in toluene, Time= 24h, T= 20 °C , Addition, Product distribution, Further Variations: Reagents, Solvents, Temperatures Imai, Yoshitane; Matsuo, Shigeaki; Zhang, Wanbin; Nakatsuji, Yohji; Ikeda, Isao; Synlett; nb. 2; (2000); p. 239 - 241

44/258

2018-07-03 17:29:03

View in Reaxys With titanium(IV) isopropylate, CPG-bound TADDOL in toluene, T= -20 °C , Addition, Product distribution, Kinetics, Further Variations: Catalysts Heckel, Alexander; Seebach, Dieter; Angewandte Chemie - International Edition; vol. 39; nb. 1; (2000); p. 163 - 165 View in Reaxys With 3,7-bis[(1'S,2'R)-2'-OH-1'-Me-2'-PhEt]-3,7-diaza-C7H12N2 in hexane, toluene, Time= 24h, T= 0 °C , Addition, Title compound not separated from byproducts Spieler, Jan; Huttenloch, Oliver; Waldmann, Herbert; European Journal of Organic Chemistry; nb. 3; (2000); p. 391 - 399 View in Reaxys With (1R,2S)-1-(1-naphthyl)-2-[N-(9'-phenylfluoren-9'-yl)amino]propan-1-ol in hexane, toluene, Addition Paleo, M. Rita; Cabeza, Isabel; Sardina, F. Javier; Journal of Organic Chemistry; vol. 65; nb. 7; (2000); p. 2108 - 2113 View in Reaxys With camphor substituted 2,2'-bipyridine in toluene, Time= 1h, T= 0 °C , Addition, Title compound not separated from byproducts Kwong, Hoi-Lun; Lee, Wing-Sze; Tetrahedron Asymmetry; vol. 10; nb. 19; (1999); p. 3791 - 3801 View in Reaxys With 1-[(S)-4-t-Bu-2,5-oxazolinyl]-1'-(η-Ph2(OH)CH)ferrocene in hexane, toluene, T= 0 °C , Addition, Title compound not separated from byproducts Deng, Wei-Ping; Hou, Xue-Long; Dai, Li-Xin; Tetrahedron Asymmetry; vol. 10; nb. 24; (1999); p. 4689 - 4693 View in Reaxys With ephedrine, Time= 24h, T= 20 °C , Addition, Title compound not separated from byproducts Sung, David W. L.; Hodge, Philip; Stratford, Peter W.; Journal of the Chemical Society - Perkin Transactions 1; nb. 11; (1999); p. 1463 - 1472 View in Reaxys With menthone substituted 2,2'-bipyridine ligand in toluene, Time= 3h, T= 0 °C , Addition, Title compound not separated from byproducts Kwong, Hoi-Lun; Lee, Wing-Sze; Tetrahedron Asymmetry; vol. 10; nb. 19; (1999); p. 3791 - 3801 View in Reaxys With 1-[(R)-4-phenyl-2,5-oxazolinyl]-1'-(η-Ph2(OH)CH)ferrocene in hexane, toluene, T= 0 °C , Addition, Title compound not separated from byproducts Deng, Wei-Ping; Hou, Xue-Long; Dai, Li-Xin; Tetrahedron Asymmetry; vol. 10; nb. 24; (1999); p. 4689 - 4693 View in Reaxys With chiral amino bicyclo[2.2.1]heptyl alcohol in toluene, Time= 24h, T= 20 °C , Addition Hanyu, Naoto; Mino, Takashi; Sakamoto, Masami; Fujita, Tsutomu; Tetrahedron Letters; vol. 41; nb. 23; (2000); p. 4587 4590 View in Reaxys With (S)-valinol-based chiral dimeric derivative in hexane, Addition Okaniwa, Masanori; Yanada, Reiko; Ibuka, Toshiro; Tetrahedron Letters; vol. 41; nb. 7; (2000); p. 1047 - 1050 View in Reaxys With 2-Ph2COH-1,1'-N,N,N',N'-tetraisopropylferrocenedicarboxamide in hexane, T= 20 °C , Addition, Product distribution, Further Variations: Reagents, Solvents Laufer, Radoslaw S.; Veith, Ulrich; Taylor, Nicholas J.; Snieckus, Victor; Organic Letters; vol. 2; nb. 5; (2000); p. 629 - 631 View in Reaxys With titanium(IV) isopropylate, (1S,2R,4S)-2-N-benzylaminomesyl-1-aminomesylcamphor in toluene, Time= 2h, T= -20 °C , Addition, Product distribution, Further Variations: Catalysts, Solvents

45/258

2018-07-03 17:29:03

Prieto, Oscar; Ramon, Diego J.; Yus, Miguel; Tetrahedron Asymmetry; vol. 11; nb. 7; (2000); p. 1629 - 1644 View in Reaxys With titanium(IV) isopropylate, (1S,2R,4S)-2-N-benzylaminomesyl-1-aminomesylcamphor in toluene, Time= 2h, T= -20 °C , Condensation, Title compound not separated from byproducts Prieto, Oscar; Ramon, Diego J.; Yus, Miguel; Tetrahedron Asymmetry; vol. 11; nb. 7; (2000); p. 1629 - 1644 View in Reaxys With titanium(IV) isopropylate, (1R,2R)-diaminocyclohexan-bis(diphenylselenophosphoramide) in hexane, toluene, Time= 24h, T= -50 °C , Addition, Title compound not separated from byproducts Shi, Min; Sui, Wen-Sheng; Tetrahedron Asymmetry; vol. 11; nb. 3; (2000); p. 835 - 841 View in Reaxys Stage 1: With dimethylamino-(R,R)-TADDOL in hexane, Time= 0.5h, T= 0 °C , complexation Stage 2: in hexane, Time= 24h, T= 0 °C , Addition, Title compound not separated from byproducts Qian, Chang-Tao; Gao, Fei-Feng; Sun, Jie; Tetrahedron Asymmetry; vol. 11; nb. 8; (2000); p. 1733 - 1740 View in Reaxys Stage 1: With methylamino-(R,R)-TADDOL in hexane, Time= 0.5h, T= 0 °C , complexation Stage 2: in hexane, Time= 24h, T= 0 °C , Addition, Title compound not separated from byproducts Qian, Chang-Tao; Gao, Fei-Feng; Sun, Jie; Tetrahedron Asymmetry; vol. 11; nb. 8; (2000); p. 1733 - 1740 View in Reaxys With Zn(II)-L-Val-L-Val in tetrahydrofuran, T= -78 - 20 °C , Condensation, Title compound not separated from byproducts Dangel, Brian D.; Polt, Robin; Organic Letters; vol. 2; nb. 19; (2000); p. 3003 - 3006 View in Reaxys With Zn(II)-L-Val-L-Val in tetrahydrofuran, T= -78 - 20 °C , Condensation, Product distribution, Further Variations: Reagents Dangel, Brian D.; Polt, Robin; Organic Letters; vol. 2; nb. 19; (2000); p. 3003 - 3006 View in Reaxys With chiral polymer-supported Ti-complex of substituted BINOL in dichloromethane, Time= 24h, T= 0 °C , Addition, Product distribution, Further Variations: Catalysts, further aldehydes Yang, Xiaowu; Su, Wu; Liu, Daxue; Wang, Hengshan; Shen, Jianheng; Da, Chaoshan; Wang, Rui; Chan, Albert S.C.; Tetrahedron; vol. 56; nb. 22; (2000); p. 3511 - 3516 View in Reaxys With chiral polymer-supported Ti-complex of substituted S-BINOL in dichloromethane, Time= 24h, T= 0 °C , Addition, Title compound not separated from byproducts Yang, Xiaowu; Su, Wu; Liu, Daxue; Wang, Hengshan; Shen, Jianheng; Da, Chaoshan; Wang, Rui; Chan, Albert S.C.; Tetrahedron; vol. 56; nb. 22; (2000); p. 3511 - 3516 View in Reaxys With chiral polymer-supported Ti-complex of substituted R-BINOL in dichloromethane, Time= 35h, T= 0 °C , Addition, Title compound not separated from byproducts Yang, Xiaowu; Su, Wu; Liu, Daxue; Wang, Hengshan; Shen, Jianheng; Da, Chaoshan; Wang, Rui; Chan, Albert S.C.; Tetrahedron; vol. 56; nb. 22; (2000); p. 3511 - 3516 View in Reaxys Stage 1: With titanium(IV) isopropylate, polymer of (R)-1,1'-binaphthol with p-C6H4(NH2)2 in hexane, dichloromethane, Time= 15h, T= 20 °C , activation Stage 2: in hexane, dichloromethane, Time= 5h, T= 0 °C , Addition, Title compound not separated from byproducts Dong, Chune; Zhang, Junlong; Zheng, Weizhong; Zhang, Liangfu; Yu, Zuolong; Choi, Michael C.K.; Chan, Albert S.C.; Tetrahedron Asymmetry; vol. 11; nb. 12; (2000); p. 2449 - 2454 View in Reaxys With 6-methylene-(S)-Troeger's base in toluene, T= 20 °C , Addition, Title compound not separated from byproducts

46/258

2018-07-03 17:29:03

Harmata, Michael; Kahraman, Mehmet; Tetrahedron Asymmetry; vol. 11; nb. 14; (2000); p. 2875 - 2879 View in Reaxys With chiral 1,4-aminoalcohol in hexane, toluene, Time= 3h, T= 20 °C , Addition, Title compound not separated from byproducts Hanyu, Naoto; Aoki, Tasuku; Mino, Takashi; Sakamoto, Masami; Fujita, Tsutomu; Tetrahedron Asymmetry; vol. 11; nb. 14; (2000); p. 2971 - 2979 View in Reaxys Stage 1: With titanium(IV) isopropylate, chiral Ti-alkoxide in toluene, Time= 0.666667h, T= 20 °C , complexation Stage 2: With titanium(IV) isopropylate in toluene, Time= 20h, T= -20 °C , Alkylation, Title compound not separated from byproducts Kostova, Kalina; Genov, Miroslav; Philipova, Irena; Dimitrov, Vladimir; Tetrahedron Asymmetry; vol. 11; nb. 16; (2000); p. 3253 - 3256 View in Reaxys With 2-<(1R)-phenyl-(<(1'R)-1'-phenylethyl>amino)methyl>phenol in toluene, Time= 3h, T= 20 °C , Alkylation, Title compound not separated from byproducts Palmieri, Gianni; Tetrahedron Asymmetry; vol. 11; nb. 16; (2000); p. 3361 - 3373 View in Reaxys With (S,S,S)-1-phenethyl-2,4-bis(1-hydroxycyclopentyl)azetidine, Time= 6h, T= 0 °C , Addition, Title compound not separated from byproducts Wilken, Joerg; Erny, Silke; Wassmann, Suzanne; Martens, Juergen; Tetrahedron Asymmetry; vol. 11; nb. 10; (2000); p. 2143 - 2148 View in Reaxys With (S,R,R)-1-phenethyl-2,4-bis(1-hydroxycyclopentyl)azetidine, Time= 6h, T= 0 °C , Addition, Title compound not separated from byproducts Wilken, Joerg; Erny, Silke; Wassmann, Suzanne; Martens, Juergen; Tetrahedron Asymmetry; vol. 11; nb. 10; (2000); p. 2143 - 2148 View in Reaxys With 3-deoxy-3-N,N-di-n-octylamino-1,2;5,6-di-O-iPr-D-altritol in toluene, Time= 12h, T= 0 °C , Addition, Title compound not separated from byproducts Cho, Byung Tae; Chun, Yu Sung; Yang, Weon Ki; Tetrahedron Asymmetry; vol. 11; nb. 10; (2000); p. 2149 - 2157 View in Reaxys With chiral hexahydro-1H-pyrrolo[1,2-c]imidazole-1-one derivative in toluene, Time= 72h, T= -5 °C , Product distribution, Further Variations: Catalysts Uozumi, Yasuhiro; Mizutani, Kanako; Nagai, Shin-ichi; Tetrahedron Letters; vol. 42; nb. 3; (2001); p. 407 - 410 View in Reaxys With 1-[1(S)-dimethylaminoethyl]-2(RP)-formylferrocene in hexane, toluene, Time= 15h, T= 0 °C , Addition, Product distribution, Further Variations: Reagents Fukuzawa, Shin-Ichi; Tsuchiya, Daisuke; Sasamoto, Kae; Hirano, Kohki; Ohtaguchi, Makoto; European Journal of Organic Chemistry; nb. 16; (2000); p. 2877 - 2883 View in Reaxys With pentaphenyl-ferrocene deriv in hexane, toluene, Time= 24h Jones; Butler; Richards; Tetrahedron Letters; vol. 41; nb. 48; (2000); p. 9351 - 9354 View in Reaxys With threo Bn2NCH(CH3)CH(OH)(Ferrocene) in toluene, Time= 5h, T= 20 °C , Alkylation, Product distribution, Further Variations: Catalysts, Temperatures Bastin; Brocard; Pelinski; Tetrahedron Letters; vol. 41; nb. 38; (2000); p. 7303 - 7307

47/258

2018-07-03 17:29:03

View in Reaxys With (S)-diphenylprolinol, (-)-1-piperidino-3,3-dimethyl-2-butanol in hexane, dichloromethane, Time= 48h, T= -40 °C , Title compound not separated from byproducts Long, Jiang; Ding, Kuiling; Angewandte Chemie - International Edition; vol. 40; nb. 3; (2001); p. 544 - 547 View in Reaxys Stage 1: With (S)-3-methyl-2-[(2-pyridylmethyl)amino]-1,1-diphenylbutan-1-ol in hexane, toluene, Time= 1h, T= 20 °C , complexation Stage 2: in hexane, toluene, Time= 5h, T= 20 °C , Addition, Title compound not separated from byproducts Wu, Yangjie; Yun, Hongying; Wu, Yusheng; Ding, Kuiling; Zhou, Ying; Tetrahedron Asymmetry; vol. 11; nb. 17; (2000); p. 3543 - 3552 View in Reaxys With (+)-camphor derivative linked to dipropylamine in hexane, toluene, Time= 2h, T= 20 °C , Addition, Title compound not separated from byproducts Hanyu, Naoto; Aoki, Tasuku; Mino, Takashi; Sakamoto, Masami; Fujita, Tsutomu; Tetrahedron Asymmetry; vol. 11; nb. 20; (2000); p. 4127 - 4136 View in Reaxys With (-)-fenchone derivative linked to morpholine in hexane, toluene, Time= 2h, T= 20 °C , Addition, Title compound not separated from byproducts Hanyu, Naoto; Aoki, Tasuku; Mino, Takashi; Sakamoto, Masami; Fujita, Tsutomu; Tetrahedron Asymmetry; vol. 11; nb. 20; (2000); p. 4127 - 4136 View in Reaxys With 1,1-diethyl-3-(3'-indolyl)-(2S)-(N-methyl-N-3'',3''-dimethylbutylamino)-1-propanol in hexane, toluene, Time= 96h, T= 20 °C , Addition, Title compound not separated from byproducts Dai, Wei-Min; Zhu, Hua-Jie; Hao, Xiao-Jiang; Tetrahedron Asymmetry; vol. 11; nb. 11; (2000); p. 2315 - 2337 View in Reaxys With (R,R)-1,2-bis(tosylamino)cyclohexane, titanium(IV) isopropylate in toluene, Time= 1h, T= -45 °C , Product distribution, Further Variations: Reagents Balsells, Jaume; Betancort, Juan M.; Walsh, Patrick J.; Angewandte Chemie - International Edition; vol. 39; nb. 19; (2000); p. 3428 - 3430 View in Reaxys With (1S,2R)-(-)-2-(N,N-di-n-butylamino)-1-phenylpropan-1-ol, Time= 2h, T= 0 °C , Product distribution, Further Variations: Reagents, Temperatures, reaction time Sato; Saito; Soai; Chemical Communications; nb. 24; (2000); p. 2471 - 2472 View in Reaxys Stage 1: With (1R,2S)-1-phenyl-2-(propylamino)propan-1-ol, T= 0 °C , Addition Stage 2: With hydrogenchloride, Hydrolysis Abramson; Lasperas; Galarneau; Desplantier-Giscard; Brunel; Chemical Communications; nb. 18; (2000); p. 1773 - 1774 View in Reaxys With C2-symmetric chiral tetrasubstituted ferrocene ligand in toluene, Time= 24h, T= 0 °C , Addition, Product distribution, Further Variations: Reaction partners, reaction time Zhang; Yoshinaga; Imai; Kida; Nakatsuji; Ikeda; Synlett; nb. 10; (2000); p. 1512 - 1514 View in Reaxys With titanium(IV) isopropylate, Ti(OiPr)2*(S)-6,6'-bis(4-vinylphenyl)-1,1'-bi-2-naphtolate in toluene, Time= 2h, T= -20 °C , Addition, Product distribution, Further Variations: Reagents Sellner, Holger; Faber, Claude; Beat Rheiner; Seebach, Dieter; Chemistry - A European Journal; vol. 6; nb. 20; (2000); p. 3692 - 3705

48/258

2018-07-03 17:29:03

View in Reaxys With (1R,3R,6S,7S)3(2OHMePh)5diPh4oxa-2azatricyclo[5.2.1.0]decane in hexane, toluene, Time= 7h, T= 20 °C Nakano, Hiroto; Okuyama, Yuko; Iwasa, Kazuto; Hongo, Hiroshi; Heterocycles; vol. 54; nb. 1; (2001); p. 411 - 418 View in Reaxys With (1S,2S)-3-tert-butyl-2-(pyrazol-1-yl)cyclohexanol in hexane, Time= 30h, T= 0 °C Glas, Holger; Barz, Michael; Thiel, Werner R.; Journal of Organometallic Chemistry; vol. 621; nb. 1-2; (2001); p. 153 - 157 View in Reaxys With C20H25NO in hexane, toluene, T= 0 - 20 °C , Product distribution, Further Variations: Solvents, Temperatures, Reagents Xu, Qianyong; Wang, Guoxing; Pan, Xinfu; Chan, Albert S.C.; Tetrahedron Asymmetry; vol. 12; nb. 3; (2001); p. 381 - 385 View in Reaxys With (2S,1'S,2'S)-Fe(CO)3[CH3CH=CH-CH=CH-CH(Et)-NHCH(Me)COH(Ph)2] in toluene, Time= 78h, T= 0 °C , Title compound not separated from byproducts Okamoto, Kazuya; Kimachi, Tetsutaro; Ibuka, Toshiro; Takemoto, Yoshiji; Tetrahedron Asymmetry; vol. 12; nb. 3; (2001); p. 463 - 467 View in Reaxys With (2S,1'S,2'S)-Fe(CO)3[CH3CH=CH-CH=CH-CH(Et)NHCH(iPr)COH(Ph)2] in toluene, Time= 45h, T= 0 °C , Title compound not separated from byproducts Okamoto, Kazuya; Kimachi, Tetsutaro; Ibuka, Toshiro; Takemoto, Yoshiji; Tetrahedron Asymmetry; vol. 12; nb. 3; (2001); p. 463 - 467 View in Reaxys With 13R-[HOCPh2]-4S-[4S-i-Pr-Δ2-oxazolin-2-yl][2.2]paracyclo in toluene, Time= 9h, Title compound not separated from byproducts Wu, Xun-Wei; Hou, Xue-Long; Dai, Li-Xin; Tao, Ju; Cao, Bo-Xun; Sun, Jie; Tetrahedron Asymmetry; vol. 12; nb. 4; (2001); p. 529 - 532 View in Reaxys With 13S-(HOCPh2)-4R-[4R-Ph-Δ2-oxazolin-2-yl][2.2]paracycloph in toluene, Time= 18h, Title compound not separated from byproducts Wu, Xun-Wei; Hou, Xue-Long; Dai, Li-Xin; Tao, Ju; Cao, Bo-Xun; Sun, Jie; Tetrahedron Asymmetry; vol. 12; nb. 4; (2001); p. 529 - 532 View in Reaxys With (R,R) bis[(N-p-tolyloxazolidin-2-yl)methylsulfide] in hexane, toluene, Time= 30h, T= 0 °C , Title compound not separated from byproducts Braga, Antonio L; Appelt, Helmoz R; Schneider, Paulo H; Rodrigues, Oscar E.D; Silveira, Claudio C; Wessjohann, Ludger A; Tetrahedron; vol. 57; nb. 16; (2001); p. 3291 - 3295 View in Reaxys Stage 1: With titanium(IV) isopropylate, (Ra)-5,6,7,8-tetrahydro-[1,1']binaphthalenyl-2,2'-diol in hexane, dichloromethane, Time= 0.25h, T= 20 °C Stage 2: in dichloromethane, Time= 5h, T= 0 °C , Title compound not separated from byproducts Shen, Xiaoqiang; Guo, Hui; Ding, Kuiling; Tetrahedron Asymmetry; vol. 11; nb. 21; (2000); p. 4321 - 4327 View in Reaxys Stage 1: With (R)-2,2-diethyl-4-(1-methylethoxy)carbonylthiazolidine in hexane, toluene, Time= 0.333333h, T= 0 °C Stage 2: in hexane, toluene, Time= 48h, T= 0 - 20 °C , Title compound not separated from byproducts Meng, Qinglin; Li, Yuelan; He, Yan; Guan, Yedi; Tetrahedron Asymmetry; vol. 11; nb. 21; (2000); p. 4255 - 4261 View in Reaxys With (2S,5R)-1-(2'-N,N-dimethylaminoethyl)-2-iso-propyl-5-methylcyclohexan-1-ol in hexane, Time= 22h, Product distribution, Further Variations: Reagents

49/258

2018-07-03 17:29:03

Panev, Stefan; Linden, Anthony; Dimitrov, Vladimir; Tetrahedron Asymmetry; vol. 12; nb. 9; (2001); p. 1313 - 1321 View in Reaxys With titanium(IV) isopropylate, (R,R)-1,2-diphenylethylenediamine, N,N'-[[(phenylmethyl)imino]bis[(1S)-1-(1-methylethyl)-2,1-ethanediyl]]bis[1,1,1-trifluoro]methanesulfonamide in toluene, Time= 90h, T= -35 °C , Product distribution, Further Variations: Reagents, amount of reagents and reaction partners; reaction time Lake, Fredrik; Moberg, Christina; Tetrahedron Asymmetry; vol. 12; nb. 5; (2001); p. 755 - 760 View in Reaxys With (S)-6-methyl-3-(2-phenylethyl)-1-phenyl-4-piperidino-3-heptanol in hexane, Time= 12h, T= 0 °C , Product distribution, Further Variations: Reagents Ohga, Takahiko; Umeda, Satoshi; Kawanami, Yasuhiro; Tetrahedron; vol. 57; nb. 23; (2001); p. 4825 - 4829 View in Reaxys With (S)-1,1'-binaphthalene-2,2'-[CH2N(CH2CPh2OH)CH2] in hexane, toluene, Time= 0.5h, T= 20 °C , Title compound not separated from byproducts Superchi, Stefano; Mecca, Tommaso; Giorgio, Egidio; Rosini, Carlo; Tetrahedron Asymmetry; vol. 12; nb. 8; (2001); p. 1235 - 1239 View in Reaxys With (1R,2S)-N-[4-tris(perfluorohexylethyl)methyl]benzylephedrine in hexane, toluene, Time= 20h, T= 20 °C , Title compound not separated from byproducts Nakamura, Yutaka; Takeuchi, Seiji; Okumura, Kazuo; Ohgo, Yoshiaki; Tetrahedron; vol. 57; nb. 26; (2001); p. 5565 - 5571 View in Reaxys With bis-L-prolinol-N-o-C6H4(CH2)2 in toluene, T= 0 °C Xu, Qianyong; Wang, Hui; Pan, Xinfu; Chan, Albert S.C; Yang, Teng-Kuei; Tetrahedron Letters; vol. 42; nb. 35; (2001); p. 6171 - 6173 View in Reaxys With (S,R)-diphenyl[1-(1-phenylethyl)-azetidin-2-yl]methanol in hexane, toluene, T= 20 °C Hermsen; Cremers; Thijs; Zwanenburg; Tetrahedron Letters; vol. 42; nb. 25; (2001); p. 4243 - 4245 View in Reaxys With titanium(IV) isopropylate, (1R,1'R)-biindenyl-(2S,2'S)-diol in hexane, Time= 10h, T= 0 - 20 °C Yang, Xiao-Wu; Shen, Jian-Heng; Da, Chao-Shan; Wang, Heng-Shan; Su, Wu; Liu, Da-Xue; Wang, Rui; Choi, Michael C.K.; Chan, Albert S.C.; Tetrahedron Letters; vol. 42; nb. 37; (2001); p. 6573 - 6575 View in Reaxys With (1S,2S,4R)-1-methyl-4-(1-methylethenyl)-2-(1-pyrrolidinyl). in toluene, Time= 24h, T= 0 - 20 °C , Title compound not separated from byproducts Chrisman, Will; Camara, Jason N.; Marcellini, Kim; Singaram, Bakthan; Goralski, Christian T.; Hasha, Dennis L.; Rudolf, Philip R.; Nicholson, Lawrence W.; Borodychuk, Karen K.; Tetrahedron Letters; vol. 42; nb. 34; (2001); p. 5805 - 5807 View in Reaxys in toluene, Time= 24h, T= 0 - 20 °C , enantiomer excess improvement, Product distribution, Further Variations: various chiral ηamino alcohol auxiliaries used Chrisman, Will; Camara, Jason N.; Marcellini, Kim; Singaram, Bakthan; Goralski, Christian T.; Hasha, Dennis L.; Rudolf, Philip R.; Nicholson, Lawrence W.; Borodychuk, Karen K.; Tetrahedron Letters; vol. 42; nb. 34; (2001); p. 5805 - 5807 View in Reaxys With C38H56N4O4 in toluene, Time= 15h, T= -35 °C , Title compound not separated from byproducts DiMauro, Erin F.; Kozlowski, Marisa C.; Organic Letters; vol. 3; nb. 19; (2001); p. 3053 - 3056 View in Reaxys With trans-2-exo-3-endo-C16H23NO in hexane, toluene, Time= 4h, T= 22 °C , Title compound not separated from byproducts

50/258

2018-07-03 17:29:03

Nevalainen, Marta; Nevalainen, Vesa; Tetrahedron Asymmetry; vol. 12; nb. 12; (2001); p. 1771 - 1777 View in Reaxys With trans-2-exo-3-endo-C16H23NO in hexane, toluene, Time= 4h, T= 22 °C , Product distribution, Further Variations: Reagents, Temperatures, Solvents Nevalainen, Marta; Nevalainen, Vesa; Tetrahedron Asymmetry; vol. 12; nb. 12; (2001); p. 1771 - 1777 View in Reaxys With titanium(IV) isopropylate, Ti(R,R)bis[Ph2(OH)C]3Me-1,3dioxolan2-yl-C6H4-pCH2CH2-PEfiber in toluene, Time= 19h, T= -25 - -20 °C , Product distribution, Further Variations: Reagents Degni, Sylvestre; Wilen, Carl-Eric; Leino, Reko; Organic Letters; vol. 3; nb. 16; (2001); p. 2551 - 2554 View in Reaxys With (1-[(S)-phenyl(((1’S)-1’-phenylethyl)amino)methyl]-2-naphthol) in hexane, toluene, Time= 24h, T= 20 °C , Product distribution, Further Variations: Reagents Liu, Da-Xue; Zhang, Li-Cheng; Wang, Quan; Da, Chao-Shan; Xin, Zhuo-Qun; Wang, Rui; Choi, Michael C. K.; Chan, Albert S. C.; Organic Letters; vol. 3; nb. 17; (2001); p. 2733 - 2735 View in Reaxys With trans-1,2-cyclohexanediamine in toluene, Time= 16h, T= -30 °C , Title compound not separated from byproducts Cobb, Alexander J. A.; Marson, Charles M.; Tetrahedron Asymmetry; vol. 12; nb. 11; (2001); p. 1547 - 1550 View in Reaxys With 1,4-di(1'-indolyl)-2R,3R-di(4-O2N-C6H4-SO2NH-)butane in toluene, Product distribution, Further Variations: Reagents McNulty; Mo; Capretta; Frampton; Chemical Communications; nb. 22; (2001); p. 2384 - 2385 View in Reaxys With (RFc,RS)-2-(p-Tolylamino)-1-tert-butylsulfinylferrocene in toluene, T= -20 °C , Product distribution, Further Variations: Reagents, Temperatures Priego; Garcia Mancheno; Cabrera; Carretero; Chemical Communications; nb. 19; (2001); p. 2026 - 2027 View in Reaxys With N-Bromosuccinimide, dimethylsulfide, 4,6-bis[((S)-prolinyl)methyl]dibenzofurane in dichloromethane, Time= 48h, T= 0 °C Ooi, Takashi; Saito, Akira; Maruoka, Keiji; Chemistry Letters; nb. 11; (2001); p. 1108 - 1109 View in Reaxys With chiral 2-azanorbornyloxazolidine deriv in hexane, toluene, Time= 7h, T= 20 °C Nakano, Hiroto; Okuyama, Yuko; Fushimi, Kazuyuki; Yamakawa, Ryo; Kayaoka, Daisuke; Hongo, Hiroshi; Heterocycles; vol. 56; nb. 1-2; (2002); p. 457 - 466 View in Reaxys With (S)-bis[N-(2-OH-1-Me-2,2-Ph2)ethyl-N-Me]-1,1'-FcmethyldiNH2 in hexane, toluene, T= 20 °C , Title compound not separated from byproducts Bastin, Stephanie; Agbossou-Niedercorn, Francine; Brocard, Jacques; Pelinski, Lydie; Tetrahedron Asymmetry; vol. 12; nb. 17; (2001); p. 2399 - 2408 View in Reaxys With (1S,2S)-bis[N-(2-OH-1-Me-2-Ph)ethyl-N-Me]-1,1'-FcmethyldiNH2 in hexane, toluene, T= 20 °C , Title compound not separated from byproducts Bastin, Stephanie; Agbossou-Niedercorn, Francine; Brocard, Jacques; Pelinski, Lydie; Tetrahedron Asymmetry; vol. 12; nb. 17; (2001); p. 2399 - 2408 View in Reaxys With 2,2-bis(4S-hydroxymethyl-5R-phenyl-2-oxazolin-2-yl)propane in hexane, toluene, Time= 45h, T= 0 °C , Product distribution, Further Variations: Reagents, reaction times

51/258

2018-07-03 17:29:03

Schinnerl, Marina; Seitz, Michael; Kaiser, Anja; Reiser, Oliver; Organic Letters; vol. 3; nb. 26; (2001); p. 4259 - 4262 View in Reaxys With (SpS)-[2.2]paracyclophane N,O-ligand in hexane, toluene, Time= 12h, T= 0 °C , Product distribution, Further Variations: Catalysts Dahmen, Stefan; Braese, Stefan; Chemical Communications; nb. 1; (2002); p. 26 - 27 View in Reaxys With (R)-methylbenzyl-N-imidazolidine disulfide from L-cystine in toluene, Time= 48h, T= 0 °C Braga, Antonio L; Vargas, Fabricio; Silveira, Claudio C; De Andrade, Leandro H; Tetrahedron Letters; vol. 43; nb. 13; (2002); p. 2335 - 2337 View in Reaxys With (R)-BINOL + Ti(OiPr)4 in toluene, Time= 24h, T= 0 °C , Product distribution, Further Variations: Catalysts Fan, Qing-Hua; Liu, Guo-Hua; Deng, Guo-Jun; Chen, Xiao-Min; Chan, Albert S.C.; Tetrahedron Letters; vol. 42; nb. 51; (2001); p. 9047 - 9050 View in Reaxys With poly(binaphthyl zinc-salen complex) in tetrahydrofuran, Time= 24h, T= 20 °C , Title compound not separated from byproducts Furusho, Yoshio; Maeda, Takeshi; Takeuchi, Takeshi; Makino, Nobuaki; Takata, Toshikazu; Chemistry Letters; nb. 10; (2001); p. 1020 - 1021 View in Reaxys With titanium(IV) isopropylate, chiral tetradentate bis-oxazoline ligand in hexane, toluene, Time= 6h, T= -15 °C , Product distribution, Further Variations: Reagents Pastor, Isidro M; Adolfsson, Hans; Tetrahedron Letters; vol. 43; nb. 9; (2002); p. 1743 - 1746 View in Reaxys 75 % Chromat., 25 % Chromat.

With ephedrine in toluene, Time= 12h, T= 20 °C , Title compound not separated from byproducts Hu, Qiao-Sheng; Sun, Chaode; Monaghan, Colleen E; Tetrahedron Letters; vol. 43; nb. 6; (2002); p. 927 - 930 View in Reaxys With titanium(IV) isopropylate, (S)-Mandelic acid in dichloromethane, T= 20 °C , Product distribution, Further Variations: Temperatures, further chiral η-hydroxy acids as ligands Bauer, Tomasz; Tarasiuk, Joanna; Tetrahedron Letters; vol. 43; nb. 4; (2002); p. 687 - 689 View in Reaxys With (S,S)-2,6-bis(2-hydroxy-2,2-dimethylpropyl)pyridine in hexane, Time= 15h, T= 20 °C , Product distribution, Further Variations: Reagents, Solvents Le Goanvic, David; Holler, Michel; Pale, Patrick; Tetrahedron Asymmetry; vol. 13; nb. 2; (2002); p. 119 - 121 View in Reaxys With (1S,2S,5R)-2-isopropyl-5-methyl-1-[(6-methyl-2-pyridinyl)methyl]cyclohexanol in hexane, Time= 15h, T= 20 °C , Title compound not separated from byproducts Le Goanvic, David; Holler, Michel; Pale, Patrick; Tetrahedron Asymmetry; vol. 13; nb. 2; (2002); p. 119 - 121 View in Reaxys With campheyl-derived 6-methylpyridine ligand in hexane, Time= 15h, T= 20 °C , Title compound not separated from byproducts Le Goanvic, David; Holler, Michel; Pale, Patrick; Tetrahedron Asymmetry; vol. 13; nb. 2; (2002); p. 119 - 121 View in Reaxys With titanium(IV) isopropylate, [(R)-6-(4-vinylbenzyloxy)methyl-BINOL]-styrene copolymer in dichloromethane, toluene, Time= 7h, T= 0 °C , Title compound not separated from byproducts Jayaprakash, Doss; Sasai, Hiroaki; Tetrahedron Asymmetry; vol. 12; nb. 18; (2001); p. 2589 - 2595

52/258

2018-07-03 17:29:03

View in Reaxys With (2R,3S,4S,5R)-2,5-bis(benzylamino)-1,6-diphenylhexane-3,4-diol in toluene, Time= 48h, T= 20 °C , Product distribution, Further Variations: Reagents Jiang, Biao; Feng, Yan; Hang, Jian-Feng; Tetrahedron Asymmetry; vol. 12; nb. 16; (2001); p. 2323 - 2329 View in Reaxys With (1R,2S)-2-diethylamino-7,7-dimethylnorbornan-1-ol in hexane, Time= 48h, T= 25 °C , Product distribution, Further Variations: Catalysts Garcia Martinez, Antonio; Teso Vilar, Enrique; Garcia Fraile, Amelia; De Moya Cerero, Santiago; Martinez-Ruiz, Paloma; Chicharro Villas, Paloma; Tetrahedron Asymmetry; vol. 13; nb. 1; (2002); p. 1 - 4 View in Reaxys With methylmagnesium bromide, (+)-8-[N,N-bis(ferrocenylmethyl)amino]menthol in diethyl ether, toluene, Time= 20h, T= 20 °C , Product distribution, Further Variations: Catalysts Vilaplana, Maria J.; Molina, Pedro; Arques, Antonio; Andres, Celia; Pedrosa, Rafael; Tetrahedron Asymmetry; vol. 13; nb. 1; (2002); p. 5 - 8 View in Reaxys With N-[2-(4-isopropyl-4,5-dihydrooxazol-2-yl)cyclohexyl]NHMs in hexane, T= 0 °C , Title compound not separated from byproducts Wipf, Peter; Wang, Xiaodong; Organic Letters; vol. 4; nb. 7; (2002); p. 1197 - 1199 View in Reaxys With (RFc,RS)-1-(t-BuSO)-2-(p-tolylsulfonylamino)ferrocene in toluene, Time= 96h, T= -20 °C , Title compound not separated from byproducts Priego, Julian; Garcia Mancheno, Olga; Cabrera, Silvia; Carretero, Juan Carlos; Journal of Organic Chemistry; vol. 67; nb. 4; (2002); p. 1346 - 1353 View in Reaxys With ephedrine in toluene, Time= 48h, T= 0 °C , Title compound not separated from byproducts Chung, Young-Min; Rhee, Hyun-Ku; Chemical Communications; nb. 3; (2002); p. 238 - 239 View in Reaxys Stage 1: With (1R,2R,4S,6S)-2-(2-anisyl)bicyclo<2.2.2>octane-2,6-diol in diethyl ether, hexane, Time= 0.25h, T= 0 °C Stage 2: in diethyl ether, hexane, Time= 40h, T= 0 °C , Title compound not separated from byproducts Sarvary, Ian; Wan, Yiqian; Frejd, Torbjoern; Journal of the Chemical Society. Perkin Transactions 1; nb. 5; (2002); p. 645 651 View in Reaxys Stage 1: With (1R,2R,4S,6S)-2-(2-C5H4N-CH2)bicyclo[2.2.2]octane-2,6-diol in diethyl ether, hexane, Time= 0.25h, T= 0 °C Stage 2: in diethyl ether, hexane, Time= 40h, T= 0 °C , Title compound not separated from byproducts Sarvary, Ian; Wan, Yiqian; Frejd, Torbjoern; Journal of the Chemical Society. Perkin Transactions 1; nb. 5; (2002); p. 645 651 View in Reaxys With (S)-3-piperidino-1,1,1-trifluoro-2-propanol in hexane, Time= 48h, T= 0 - 20 °C , Product distribution, Further Variations: Reagents Katagiri, Toshimasa; Fujiwara, Yasuyuki; Takahashi, Satoshi; Ozaki, Nobuyuki; Uneyama, Kenji; Chemical Communications; nb. 9; (2002); p. 986 - 987 View in Reaxys With titanium(IV) isopropylate, CPG-immobilized chiral-TADDOL in toluene, T= -20 °C , Product distribution, Further Variations: Catalysts Heckel, Alexander; Seebach, Dieter; Chemistry--A European Journal; vol. 8; nb. 3; (2002); p. 559 - 572 View in Reaxys

53/258

2018-07-03 17:29:03

Stage 1: With titanium(IV) isopropylate, (R)-6,6'-diperfluorobutyl-1,1'-binaphthyl-2,2'-diol in hexane, Time= 0.25h, T= 45 °C Stage 2: in hexane, T= 45 °C , Title compound not separated from byproducts Tian, Yuan; Yang, Qing Chuan; Mak, Thomas C.W.; Chan, Kin Shing; Tetrahedron; vol. 58; nb. 20; (2002); p. 3951 - 3961 View in Reaxys Stage 1: With titanium(IV) isopropylate, (S)-6,6'-diperfluorooctyl-1,1'-binaphthyl-2,2'-diol in hexane, Time= 0.25h, T= 45 °C Stage 2: in hexane, T= 45 °C , Title compound not separated from byproducts Tian, Yuan; Yang, Qing Chuan; Mak, Thomas C.W.; Chan, Kin Shing; Tetrahedron; vol. 58; nb. 20; (2002); p. 3951 - 3961 View in Reaxys Stage 1: With titanium(IV) isopropylate, (R)-6,6'-bis[(C6F13CH2CH2)3Si]-BINOL in hexane, Time= 0.166667h, T= 20 °C Stage 2: in hexane, Time= 1h, T= 0 °C , Title compound not separated from byproducts Nakamura, Yutaka; Takeuchi, Seiji; Okumura, Kazuo; Ohgo, Yoshiaki; Curran, Dennis P; Tetrahedron; vol. 58; nb. 20; (2002); p. 3963 - 3969 View in Reaxys With (1R,2S)-(+)-2-(N,N-di-n-butylamino)-1-phenylpropan-1-ol in hexane, T= 0 °C , Title compound not separated from byproducts Wolf, Christian; Hawes, Pili A.; Journal of Organic Chemistry; vol. 67; nb. 8; (2002); p. 2727 - 2729 View in Reaxys With trans-(1S,2S)-1-phenyl-2-(N,N-dibutylamino)-1-indanol in hexane, toluene, Time= 12h, T= 0 °C , Product distribution, Further Variations: Reagents Xu, Qianyong; Yang, Hongfang; Pan, Xinfu; Chan, Albert S.C.; Tetrahedron Asymmetry; vol. 13; nb. 9; (2002); p. 945 - 951 View in Reaxys With C88H128N4O4Si5 chiral dendrimer in toluene, Time= 48h, T= 0 °C , Title compound not separated from byproducts Sato, Itaru; Kodaka, Ryo; Hosoi, Kenji; Soai, Kenso; Tetrahedron Asymmetry; vol. 13; nb. 8; (2002); p. 805 - 808 View in Reaxys With zirconium(IV) tetraisopropoxide, ((R)-(-)-thiolan-2-yl)diphenylmethanol in hexane, toluene, Time= 20h, T= -78 - 0 °C , Title compound not separated from byproducts Shiina, Isamu; Konishi, Katsuhiko; Kuramoto, Yu-suke; Chemistry Letters; nb. 2; (2002); p. 164 - 165 View in Reaxys Stage 1: With (2S)-3-(4-benzyloxyphenyl)-2-butylamino-1,1-diphenylpropanol in diethyl ether, hexane, Time= 0.666667h Stage 2: in diethyl ether, hexane, Time= 16h, T= 20 °C , Title compound not separated from byproducts Wolf, Christian; Francis, Christopher J.; Hawes, Pili A.; Shah, Mirage; Tetrahedron Asymmetry; vol. 13; nb. 16; (2002); p. 1733 - 1741 View in Reaxys With (S)-(+)-2,2'-[2-(1,1-dimethyl-2,2-diphenyl-2-hydroxy-ethyl)-2-azapropane-1,3-diyl]-1,1'-binaphthalene in hexane, toluene, Time= 1h, T= 20 °C , Product distribution, Further Variations: Reagents, reaction time Superchi, Stefano; Giorgio, Egidio; Scafato, Patrizia; Rosini, Carlo; Tetrahedron Asymmetry; vol. 13; nb. 13; (2002); p. 1385 - 1391 View in Reaxys Stage 1: With (S,S,S)-[2-hydroxy-3-(2-methoxynaphthyl)naphth-1-yl]2 in toluene, Time= 0.5h Stage 2: in toluene, Time= 24h, T= 0 °C , Title compound not separated from byproducts Simonson, Duane L; Kingsbury, Kevin; Xu, Ming-Hua; Hu, Qiao-Sheng; Sabat, Michal; Pu, Lin; Tetrahedron; vol. 58; nb. 41; (2002); p. 8189 - 8193 View in Reaxys With (1R)-1-dimethylamino-2-endo-hydroxy-3,3-dimethylnorbornane in hexane, Product distribution, Further Variations: Reagents

54/258

2018-07-03 17:29:03

Garcia Martinez, Antonio; Teso Vilar, Enrique; Garcia Fraile, Amelia; De la Moya Cerero, Santiago; Martinez-Ruiz, Paloma; Tetrahedron Asymmetry; vol. 13; nb. 14; (2002); p. 1457 - 1460 View in Reaxys With (1R,2R,4S)-1-methyl-4-(1-methylethenyl)-2-(1-pyrrolidinyl)cyclohexanol in hexane, Time= 24h, T= 0 °C , Product distribution, Further Variations: Reagents Steiner, Derek; Sethofer, Steven G.; Goralski, Christian T.; Singaram, Bakthan; Tetrahedron Asymmetry; vol. 13; nb. 14; (2002); p. 1477 - 1483 View in Reaxys With (1S,2S,4R)-1-methyl-4-(1-methylethenyl)-2-(1-piperidinyl)cyclohexanol in hexane, Time= 24h, T= 0 °C , Title compound not separated from byproducts Steiner, Derek; Sethofer, Steven G.; Goralski, Christian T.; Singaram, Bakthan; Tetrahedron Asymmetry; vol. 13; nb. 14; (2002); p. 1477 - 1483 View in Reaxys With (1R,2R,4S)-1-methyl-4-(1-methylethenyl)-2-(1-piperidinyl)cyclohexanol in hexane, Time= 24h, T= 0 °C , Title compound not separated from byproducts Steiner, Derek; Sethofer, Steven G.; Goralski, Christian T.; Singaram, Bakthan; Tetrahedron Asymmetry; vol. 13; nb. 14; (2002); p. 1477 - 1483 View in Reaxys With titanium(IV) isopropylate, N,N'-[(1S,2R)-HOCHPh-C(Me)Ph-]2-1,3-benzenedisulfonamide in toluene, Time= 8h, T= 0 °C , Product distribution, Further Variations: Reaction partners, Reagents, Temperatures Yus, Miguel; Ramon, Diego J.; Prieto, Oscar; Tetrahedron Asymmetry; vol. 13; nb. 14; (2002); p. 1573 - 1579 View in Reaxys With titanium(IV) isopropylate, N,N'-di[(1S,2R)-2-hydroxy-1,2-diphenylethyl]-1,3-benzenedisulfonamide in toluene, Time= 8h, T= 0 °C , Title compound not separated from byproducts Yus, Miguel; Ramon, Diego J.; Prieto, Oscar; Tetrahedron Asymmetry; vol. 13; nb. 14; (2002); p. 1573 - 1579 View in Reaxys With (S)-(-)-1,1'-bi-(2-naphthyloxy)(diisopropoxy)titanium in hexane, dichloromethane, Product distribution, Further Variations: Reagents, Reaction partners, further arylaldehydes Balsells, Jaume; Davis, Timothy J.; Carroll, Patrick; Walsh, Patrick J.; Journal of the American Chemical Society; vol. 124; nb. 35; (2002); p. 10336 - 10348 View in Reaxys With N,N'-bis(mesitylmethylene)biphenyl-2,2'-diamine, (S)-3,3'-diphenyl-2,2'-dihydroxy-1,1'-binaphthyl in dichloromethane, toluene, T= -45 °C , Product distribution, Further Variations: Reagents, Temperatures Costa, Anna M.; Jimeno, Ciril; Gavenonis, Jason; Carroll, Patrick J.; Walsh, Patrick J.; Journal of the American Chemical Society; vol. 124; nb. 24; (2002); p. 6929 - 6941 View in Reaxys With chiral MeO-PEG-supported ferrocenyl oxazoline in toluene, T= 10 °C , Title compound not separated from byproducts Bolm, Carsten; Hermanns, Nina; Classen, Arno; Muiz, Kilian; Bioorganic and Medicinal Chemistry Letters; vol. 12; nb. 14; (2002); p. 1795 - 1798 View in Reaxys With (1S,2R)-(+)-ephedrine in hexane, Time= 24h, T= 20 °C , Product distribution, Further Variations: Reagents, Temperatures, Solvents Braese, Stefan; Dahmen, Stefan; Lauterwasser, Frank; Leadbeater, Nicholas E; Sharp, Emma L; Bioorganic and medicinal chemistry letters; vol. 12; nb. 14; (2002); p. 1849 - 1851 View in Reaxys With (S)-3-PhCH2SeCH2-4-PhCH2-oxazolidine in hexane, toluene, Time= 20h, T= 20 °C , Title compound not separated from byproducts

55/258

2018-07-03 17:29:03

Braga, Antonio L.; Rodrigues, Oscar E. D.; Paixao, Marcio W.; Appelt, Helmoz R.; Silveira, Claudio C.; Bottega, Diana P.; Synthesis; nb. 16; (2002); p. 2338 - 2340 View in Reaxys With (SP)-1-[(Ph2COH)]-2-(pyrrolidin-1-ylmethyl)ferrocene in hexane, toluene, Time= 24h, T= 20 °C , Product distribution, Further Variations: Reagents Sebesta, Radovan; Salisova, Marta; Collection of Czechoslovak Chemical Communications; vol. 67; nb. 11; (2002); p. 1700 1708 View in Reaxys With chiral amino-oxazoline catalyst in dichloromethane, toluene, Time= 24h, T= 0 °C , Product distribution, Further Variations: Catalysts, Solvents, Temperatures Shaikh, Nadim S; Deshpande, Vishnu H; Bedekar, Ashutosh V; Tetrahedron Letters; vol. 43; nb. 32; (2002); p. 5587 - 5589 View in Reaxys With 2η-hydroxy-3η-aminopinane in hexane, toluene, T= 0 - 20 °C , Product distribution, Further Variations: Reagents Markowicz, Stanislaw W.; Pokrzeptowicz, Katarzyna; Karolak-Wojciechowska, Janina; Czylkowski, Robert; Omelanczuk, Jan; Sobczak, Agata; Tetrahedron Asymmetry; vol. 13; nb. 18; (2002); p. 1981 - 1991 View in Reaxys Stage 1: With 1-<(4-CH3C6H4)<methyl<1'-(Ph)ethyl>amino>methyl>-2-naphthol in toluene, T= 0 - 20 °C Stage 2: in toluene, T= 0 - 20 °C , Title compound not separated from byproducts Cimarelli, Cristina; Palmieri, Gianni; Volpini, Emanuela; Tetrahedron Asymmetry; vol. 13; nb. 22; (2002); p. 2417 - 2426 View in Reaxys With (1R,5R,6R)-6-hydroxy-6-(6-methylpyridin-2-ylmethyl)bicyclo[3.3.0]octan-2-one in hexane, toluene, Time= 28h, T= 0 20 °C , Product distribution, Further Variations: Reagents Zhong, Yu-wu; Lei, Xin-sheng; Lin, Guo-qiang; Tetrahedron Asymmetry; vol. 13; nb. 20; (2002); p. 2251 - 2255 View in Reaxys With titanium(IV) isopropylate, (R,R)-1,2-[(2,5-Me2-C6H3)SO2NH]2-cyclohexane in hexane, toluene, T= -35 °C , Product distribution, Further Variations: Reagents, Temperatures Balsells, Jaume; Costa, Anna M.; Walsh, Patrick J.; Israel Journal of Chemistry; vol. 41; nb. 4; (2001); p. 251 - 261 View in Reaxys With titanium(IV) isopropylate, [cis-(PEt3)2Pt(6,6'-Cl2-2,2'-(OH)2-4,4'-(CC)2-1,1'-binaph)]3, T= 20 °C , Title compound not separated from byproducts Lee, Suk Joong; Hu, Aiguo; Lin, Wenbin; Journal of the American Chemical Society; vol. 124; nb. 44; (2002); p. 12948 12949 View in Reaxys With chiral hydroxy imidazoline in hexane, toluene, Product distribution, Further Variations: Reagents Casey, Mike; Smyth, Martin P.; Synlett; nb. 1; (2003); p. 102 - 106 View in Reaxys With aziridin-2-yldiphenylmethanol in toluene, Time= 24h, T= 20 °C , Product distribution, Further Variations: Reagents, reaction time Bulman Page, Philip C.; Allin, Steven M.; Maddocks, Suzanne J.; Elsegood, Mark R.J.; Journal of the Chemical Society. Perkin Transactions 1; nb. 24; (2002); p. 2827 - 2832 View in Reaxys With (S)-1-(η-azepanylbenzyl)-2-naphthol in toluene, Time= 8h, T= 0 °C , Product distribution, Further Variations: Reagents, Temperatures, reaction time Lu, Jun; Xu, Xuenong; Wang, Shaozhong; Wang, Cunde; Hu, Yuefei; Hu, Hongwen; Journal of the Chemical Society. Perkin Transactions 1; nb. 24; (2002); p. 2900 - 2903 View in Reaxys

56/258

2018-07-03 17:29:03

With titanium(IV) isopropylate, chiral metallacyclophane, Time= 16h, T= 0 °C , Title compound not separated from byproducts Jiang, Hua; Hu, Aiguo; Lin, Wenbin; Chemical Communications; nb. 1; (2003); p. 96 - 97 View in Reaxys With (2R)-2-OH-2-(o-MeOC6H4-)-1,3,3-Me3-bicyclo[2.2.1]heptane in hexane, Time= 24h, T= -30 °C , Product distribution, Further Variations: Reagents Steigelmann, Melanie; Nisar, Yasmin; Rominger, Frank; Goldfuss, Bernd; Chemistry - A European Journal; vol. 8; nb. 22; (2002); p. 5211 - 5218 View in Reaxys With titanium(IV) isopropylate, 4,4'-Dihydroxybiphenyl, (1R,2R)-1,2-N,N'-bis(1-naphthylsulfonylamino)cyclohexane in hexane, Time= 50h, T= 20 °C Nagasawa, Tomomi; Miyata, Hideto; Kudo, Nozomi; Nakatani, Motoi; Ito, Kazuaki; Ohba, Yoshihiro; Heterocyclic Communications; vol. 8; nb. 5; (2002); p. 423 - 426 View in Reaxys With titanium(IV) isopropylate, N,N'-[[(phenylmethyl)imino]bis[(1S)-1-(1-methylethyl)-2,1-ethanediyl]]bis[1,1,1-trifluoro]methanesulfonamide in toluene, Time= 0.75h, T= -35 °C , Product distribution, Further Variations: Reagents, time Lake, Fredrik; Moberg, Christina; European Journal of Organic Chemistry; nb. 18; (2002); p. 3179 - 3188 View in Reaxys With 1-methyl-cis-decahydro-quinolin-7-ol in toluene, Time= 8h, T= 20 °C , Title compound not separated from byproducts Panda, Manoranjan; Phuan, Puay-Wah; Kozlowski, Marisa C.; Journal of Organic Chemistry; vol. 68; nb. 2; (2003); p. 564 - 571 View in Reaxys With D-fructose and quinoline derived chiral catalyst in toluene Huang, Hanmin; Chen, Huilin; Hu, Xinquan; Bai, Changmin; Zheng, Zhuo; Tetrahedron Asymmetry; vol. 14; nb. 3; (2003); p. 297 - 304 View in Reaxys Stage 1: With chiral tris(1,1'-binaphthyl)-based Salen-type ligand in toluene, Time= 1h, T= 20 °C Stage 2: in toluene, Time= 48h, T= 20 °C , Title compound not separated from byproducts Shi, Min; Wang, Chun-Jiang; Tetrahedron Asymmetry; vol. 13; nb. 19; (2002); p. 2161 - 2166 View in Reaxys With titanium(IV) isopropylate, polymer 7-OH in hexane, dichloromethane, Time= 20h, T= 0 °C , Product distribution, Further Variations: Catalysts Herres, Sonja; Hesemann, Peter; Moreau, Joel J. E.; European Journal of Organic Chemistry; nb. 1; (2003); p. 99 - 105 View in Reaxys With titanium(IV) isopropylate, (1S,2R,4S,1'S,2'R,4'S)-C28H44N2O6S2 (m-substituted benzene) in toluene, Time= 3h, T= 25 °C , Title compound not separated from byproducts Yus, Miguel; Ramon, Diego J.; Prieto, Oscar; Tetrahedron Asymmetry; vol. 14; nb. 9; (2003); p. 1103 - 1114 View in Reaxys With (1S,2S)-1-N-[(S)-η-phenylethyl]-η-aminocyclohexanol in hexane, toluene, Time= 20h, T= 20 °C , Product distribution, Further Variations: Reagents Sosa-Rivadeneyra, Martha; Munoz-Muniz, Omar; Anaya de Parrodi, Cecilia; Quintero, Leticia; Juaristi, Eusebio; Journal of Organic Chemistry; vol. 68; nb. 6; (2003); p. 2369 - 2375 View in Reaxys Stage 1: With (R)-3,3'-dibromo-1,1'-bi-2-naphthol, (R,R)-1,2-Ph2-N,N'-bis(mesitylmethylidene)ethane-1,2-diamine in toluene, Time= 24h, T= -20 °C Stage 2: With ammonium chloride in water, toluene, Title compound not separated from byproducts

57/258

2018-07-03 17:29:03

Du, Haifeng; Ding, Kuiling; Organic Letters; vol. 5; nb. 7; (2003); p. 1091 - 1093 View in Reaxys With (1'S-phenylethyl)-(S)-pyrrolidin-2-ylmethylamine, ditosylethylenediamine in hexane, toluene, Time= 20h, T= 0 - 20 °C , Title compound not separated from byproducts Munoz-Muniz, Omar; Juaristi, Eusebio; Journal of Organic Chemistry; vol. 68; nb. 10; (2003); p. 3781 - 3785 View in Reaxys With ditosylethylenediamine, (S)-2-<(S)-(-)-phenylethylcarbamoyl>pyrrolidine in hexane, toluene, Time= 20h, T= 0 - 20 °C , Title compound not separated from byproducts Munoz-Muniz, Omar; Juaristi, Eusebio; Journal of Organic Chemistry; vol. 68; nb. 10; (2003); p. 3781 - 3785 View in Reaxys Stage 1: With chiral C25H35NO6 in hexane, toluene, Time= 0.5h, T= 0 °C Stage 2: in hexane, toluene, Time= 12h, T= -10 °C , Title compound not separated from byproducts Huang, Hanmin; Zheng, Zhuo; Chen, Huilin; Bai, Changmin; Wang, Junwei; Tetrahedron Asymmetry; vol. 14; nb. 10; (2003); p. 1285 - 1289 View in Reaxys Stage 1: With 4η-morpholinocaran-3η-ol in toluene, Time= 30h, T= 20 °C Stage 2: in toluene, Time= 20h, T= 20 °C , Title compound not separated from byproducts Joshi, Sudhir N.; Malhotra, Sanjay V.; Tetrahedron Asymmetry; vol. 14; nb. 13; (2003); p. 1763 - 1766 View in Reaxys With titanium(IV) isopropylate, (R)-F13BINOL in hexane, Time= 1h, T= 0 °C , Product distribution, Further Variations: Reagents, Solvents, time Nakamura, Yutaka; Takeuchi, Seiji; Ohgo, Yoshiaki; Journal of Fluorine Chemistry; vol. 120; nb. 2; (2003); p. 121 - 129 View in Reaxys With (S)-ferrocenyl-CH2N(CH2-i-PrOx)Ph in toluene, Time= 72h, T= 20 °C , Product distribution, Further Variations: Catalysts Stepnicka, Petr; Base, Tomas; Cisarova, Ivana; Kubista, Jiri; Vyskocil, Stepan; Sticha, Martin; Collection of Czechoslovak Chemical Communications; vol. 68; nb. 7; (2003); p. 1206 - 1232 View in Reaxys With PEG-supported Zn(II)-salen complex with glutarate spacer in hexane, toluene, Time= 32h, T= 0 - 20 °C , Product distribution, Further Variations: Catalysts, reaction times Anyanwu, Uche K.; Venkataraman; Tetrahedron Letters; vol. 44; nb. 34; (2003); p. 6445 - 6448 View in Reaxys With chiral ligand in hexane, toluene, Time= 18h, T= 0 °C , Title compound not separated from byproducts Okuyama, Yuko; Nakano, Hiroto; Igarashi, Mayumi; Kabuto, Chizuko; Hongo, Hiroshi; Heterocycles; vol. 59; nb. 2; (2003); p. 635 - 643 View in Reaxys Stage 1: With (1R,2S)-2-((4-bromobenzyl)methylamino)-1-phenyl-1-propanol in hexane, Time= 1h, T= 20 °C Stage 2: in hexane, T= 20 °C , Title compound not separated from byproducts Edwards, Christopher W.; Haddleton, David M.; Morsley, David; Shipton, Mark R.; Wills, Martin; Tetrahedron; vol. 59; nb. 31; (2003); p. 5823 - 5830 View in Reaxys With (S)-2-(dibenzylamino)-3-phenylpropan-1-ol in toluene, Time= 24h, T= 20 °C , Product distribution, Further Variations: Reagents Ionescu, Ruxandra D.; Blom, Anna; Frejd, Torbjoern; Tetrahedron Asymmetry; vol. 14; nb. 16; (2003); p. 2369 - 2380 View in Reaxys With polystyrene-divinylbenzene supported N-methyl-S-valinol in toluene, Time= 24h, T= 25 °C , Product distribution, Further Variations: Reagents

58/258

2018-07-03 17:29:03

Burguete, M. Isabel; Collado, Manuel; Garcia-Verdugo, Eduardo; Vicent, Maria J.; Luis, Santiago V.; Von Keyserling, Nikolai Graf; Martens, Juergen; Tetrahedron; vol. 59; nb. 10; (2003); p. 1797 - 1804 View in Reaxys With 2-methyl-10-[(dimethylamino)methyl]isoborneol in toluene, T= 20 °C , Title compound not separated from byproducts Garcia Martinez, Antonio; Teso Vilar, Enrique; Garcia Fraile, Amelia; De La Moya Cerero, Santiago; Lora Maroto, Beatriz; Tetrahedron Asymmetry; vol. 14; nb. 14; (2003); p. 1959 - 1963 View in Reaxys With 10-[(dimethylamino)methyl]isoborneol in toluene, T= 20 °C , Title compound not separated from byproducts Garcia Martinez, Antonio; Teso Vilar, Enrique; Garcia Fraile, Amelia; De La Moya Cerero, Santiago; Lora Maroto, Beatriz; Tetrahedron Asymmetry; vol. 14; nb. 14; (2003); p. 1959 - 1963 View in Reaxys With N,N'-bis(o-(C6H5SO2NH)C6H4-CH=N-)-1R,2R-cyclohexane in toluene, Time= 48h, T= 25 °C , Product distribution, Further Variations: Reagents, Temperatures Fonseca, Maria Hechavarria; Eibler, Ernst; Zabel, Manfred; Koenig, Burkhard; Tetrahedron Asymmetry; vol. 14; nb. 14; (2003); p. 1989 - 1994 View in Reaxys With (Rp)-4-(HO(CH2)2N=C(Me)-)-5-OH-[2.2]paracyclophane in hexane, toluene, T= 0 - 25 °C , Product distribution, Further Variations: Reagents Danilova, Tatyana I.; Rozenberg, Valeria I.; Sergeeva, Elena V.; Starikova, Zoya A.; Braese, Stefan; Tetrahedron Asymmetry; vol. 14; nb. 14; (2003); p. 2013 - 2019 View in Reaxys With chiral cyclic diimine ligand in toluene, T= 20 °C , Title compound not separated from byproducts Fonseca, Maria Hechavarria; Hjelmgaard, Thomas; Koenig, Burkhard; Molecules; vol. 8; nb. 5; (2003); p. 453 - 458 View in Reaxys With chiral 1,3-oxazolidine zinc amide in toluene, Time= 8h, T= 0 °C , Product distribution, Further Variations: Catalysts, Temperatures Prasad; Joshi; Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry; vol. 42; nb. 1; (2003); p. 150 - 153 View in Reaxys With (1R,2S)-2-(N,N-dibenzylamino)-1-ferrocenyl-1-propanol in hexane, toluene, Time= 5h, T= 20 °C , Title compound not separated from byproducts Bastin, Stephanie; Ginj, Mihaela; Brocard, Jacques; Pelinski, Lydie; Novogrocki, Guy; Tetrahedron Asymmetry; vol. 14; nb. 12; (2003); p. 1701 - 1708 View in Reaxys With (1S,2S)-2-(N,N-dibutylamino)-1-ferrocenyl-1-propanol in hexane, toluene, Time= 1h, T= 20 °C , Title compound not separated from byproducts Bastin, Stephanie; Ginj, Mihaela; Brocard, Jacques; Pelinski, Lydie; Novogrocki, Guy; Tetrahedron Asymmetry; vol. 14; nb. 12; (2003); p. 1701 - 1708 View in Reaxys With chiral 2-pyridylmethanol derivative in toluene, Time= 20.5h, T= 0 °C Rahm, Fredrik; Fischer, Andreas; Moberg, Christina; European Journal of Organic Chemistry; nb. 21; (2003); p. 4205 4215 View in Reaxys With chiral 1,1'-bipyridine derivative in toluene, Time= 20.5h, T= 0 °C Rahm, Fredrik; Fischer, Andreas; Moberg, Christina; European Journal of Organic Chemistry; nb. 21; (2003); p. 4205 4215 View in Reaxys

59/258

2018-07-03 17:29:03

With titanium(IV) isopropylate, dendritic substituted (R)-1,1'-binaphthalene-2,2'-diol in hexane, toluene, Time= 7h, T= 0 °C , Title compound not separated from byproducts Liu, Guo-Hua; Tang, Wei-Jun; Fan, Qing-Hua; Tetrahedron; vol. 59; nb. 43; (2003); p. 8603 - 8611 View in Reaxys With [(1S)-1-((S)-1-methyl-propyl)-(2-morpholin-4-yl-ethyl)]carbamic acid methyl ester in hexane, Time= 24h, T= 4 °C , Title compound not separated from byproducts Richmond, Meaghan L.; Seto, Christopher T.; Journal of Organic Chemistry; vol. 68; nb. 19; (2003); p. 7505 - 7508 View in Reaxys With titanium(IV) isopropylate, chiral cis-Pt(PEt3)2(C22H13O2)2 in dichloromethane, toluene, Time= 16h, T= 20 °C , Title compound not separated from byproducts Hua, Jiang; Lin, Wenbin; Organic Letters; vol. 6; nb. 6; (2004); p. 861 - 864 View in Reaxys Stage 1: With SiO2-immobilized chiral amino alcohol in toluene, Time= 0.5h, T= -15 °C Stage 2: With n-butyllithium in toluene, Time= 96h, T= -25 °C , Title compound not separated from byproducts Fraile, Jose M.; Mayoral, Jose A.; Serrano, Jorge; Pericas, Miquel A.; Sola, Lluis; Castellnou, David; Organic Letters; vol. 5; nb. 23; (2003); p. 4333 - 4335 View in Reaxys With titanium(IV) isopropylate, N,N'-bis{[(1S,2R,4R)-2-hydroxy-7,7-dimethylbicyclo[2.2.1]hept-1-yl]methanesulfonyl}benzene-1,3-diamine in dichloromethane, toluene, Time= 3h, T= 20 °C , Product distribution, Further Variations: Temperatures, Reagents Bauer, Tomasz; Gajewiak, Joanna; Tetrahedron; vol. 59; nb. 50; (2003); p. 10009 - 10012 View in Reaxys With (R)-2-phenyl-4-hydroxymethyl-4,5-dihydrooxazole in hexane, toluene, Time= 24h, T= 20 °C , Title compound not separated from byproducts Braga, Antonio L.; Rubim, Rodrigo M.; Schrekker, Henri S.; Wessjohann, Ludger A.; De Bolster, Martin W. G.; Zeni, Gilson; Sehnem, Jasquer A.; Tetrahedron Asymmetry; vol. 14; nb. 21; (2003); p. 3291 - 3295 View in Reaxys With chiral 1,1'-bis(oxazolin-2-yl)ferrocene based ligand in toluene, Time= 24h, T= 20 °C , Title compound not separated from byproducts Bonini, Bianca F.; Fochi, Mariafrancesca; Comes-Franchini, Mauro; Ricci, Alfredo; Thijs, Lambertus; Zwanenburg, Binne; Tetrahedron Asymmetry; vol. 14; nb. 21; (2003); p. 3321 - 3327 View in Reaxys With 1-[4S-tBu-oxazolin-2-yl]-1'-[Ph2C(OH)]-2-(Rp)-Me-ferrocene in hexane, toluene, T= 0 °C , Title compound not separated from byproducts Li, Ming; Yuan, Ke; Li, Yang-Yang; Cao, Bo-Xun; Sun, Jie; Hou, Xue-Long; Tetrahedron Asymmetry; vol. 14; nb. 21; (2003); p. 3347 - 3352 View in Reaxys With 1-[4R-Ph-oxazolin-2-yl]-1'-[Ph2C(OH)]-2-(Sp)-Me-ferrocene in hexane, toluene, T= 0 °C , Title compound not separated from byproducts Li, Ming; Yuan, Ke; Li, Yang-Yang; Cao, Bo-Xun; Sun, Jie; Hou, Xue-Long; Tetrahedron Asymmetry; vol. 14; nb. 21; (2003); p. 3347 - 3352 View in Reaxys With titanium(IV) isopropylate, chiral BINOL-based disulfide monolayer-protected Au cluster in dichloromethane, Time= 7h, T= -10 °C , Product distribution, Further Variations: Catalysts Marubayashi, Kazuyoshi; Takizawa, Shinobu; Kawakusu, Tetsuo; Arai, Takayoshi; Sasai, Hiroaki; Organic Letters; vol. 5; nb. 23; (2003); p. 4409 - 4412

60/258

2018-07-03 17:29:03

View in Reaxys With chiral cyclic tartaric acid 1,2-diacetal in hexane, toluene, Time= 24h, T= 12 - 15 °C , Product distribution, Further Variations: Catalysts Barros, M. Teresa; Maycock, Christopher D.; Phillips, Ana Maria Faisca; European Journal of Organic Chemistry; nb. 8; (2004); p. 1820 - 1829 View in Reaxys With Boc-(S)-CH(i-Pr)-CONHCH2CH2-(morpholin-4-yl) in hexane, Time= 24h, T= 0 °C , Product distribution, Further Variations: Reagents, reaction times Sprout, Christopher M.; Seto, Christopher T.; Journal of Organic Chemistry; vol. 68; nb. 20; (2003); p. 7788 - 7794 View in Reaxys With dibenzo[a,c]cycloheptadiene based chiral bis(oxazoline) in hexane, toluene, Time= 24h, T= 0 °C , Title compound not separated from byproducts Fu, Bin; Du, Da-Ming; Wang, Jianbo; Tetrahedron Asymmetry; vol. 15; nb. 1; (2004); p. 119 - 126 View in Reaxys With 1R,2R-N-[2-(4-iPr-4,5-dihydrooxazol-2-yl)cyclohexyl]NHSO2Me in hexane, Time= 21h, T= 0 °C , Title compound not separated from byproducts Wipf, Peter; Pierce, Joshua G.; Wang, Xiaodong; Tetrahedron Asymmetry; vol. 14; nb. 22; (2003); p. 3605 - 3611 View in Reaxys With 1S,2S-N-[2-(4-iPr-4,5-dihydrooxazol-2-yl)cyclohexyl]NHSO2Me in hexane, Time= 21h, T= 0 °C , Title compound not separated from byproducts Wipf, Peter; Pierce, Joshua G.; Wang, Xiaodong; Tetrahedron Asymmetry; vol. 14; nb. 22; (2003); p. 3605 - 3611 View in Reaxys With [(S)-AHPC]EDA in hexane, toluene, Time= 15h, T= 25 °C , Title compound not separated from byproducts Danilova, Tatyana I.; Rozenberg, Valeria I.; Starikova, Zoya A.; Braese, Stefan; Tetrahedron Asymmetry; vol. 15; nb. 2; (2004); p. 223 - 229 View in Reaxys With [(R)-AHPC][(S)-FHPC](1R,2R)-CHDA in hexane, toluene, Time= 15h, T= 25 °C , Title compound not separated from byproducts Danilova, Tatyana I.; Rozenberg, Valeria I.; Starikova, Zoya A.; Braese, Stefan; Tetrahedron Asymmetry; vol. 15; nb. 2; (2004); p. 223 - 229 View in Reaxys With (S,S)-η-(2-hydroxy-1-naphthyl)-η'-methyldibenzylamine in toluene, Time= 24h, T= 0 °C , Title compound not separated from byproducts Degni, Sylvestre; Wilen, Carl-Eric; Leino, Reko; Tetrahedron Asymmetry; vol. 15; nb. 2; (2004); p. 231 - 237 View in Reaxys Stage 1: With Me 4,6-O-(=CHPh)-2-deoxy-2-(4-morpholino)-η-D-glucopyranoside in toluene, T= 20 °C Stage 2: in toluene, Time= 26h, T= 20 °C , Title compound not separated from byproducts Emmerson, Daniel P G; Villard, Renaud; Mugnaini, Claudia; Batsanov, Andrei; Howard, Judith A K; Hems, William P; Tooze, Robert P; Davis, Benjamin G; Organic and biomolecular chemistry; vol. 1; nb. 21; (2003); p. 3826 - 3838 View in Reaxys With (2S)-1-ferrocenylmethylaziridin-2-yl(diphenyl)methanol in hexane, toluene, T= 0 - 20 °C , Product distribution, Further Variations: Catalysts Wang, Min-Can; Wang, De-Kun; Zhu, Yu; Liu, Lan-Tao; Guo, Yi-Fei; Tetrahedron Asymmetry; vol. 15; nb. 8; (2004); p. 1289 - 1294 View in Reaxys

61/258

2018-07-03 17:29:03

With (1S,5S,7R)-(3-Et-6,8-dioxa-3-azabicyclo[3.2.1]oct-7-yl)CH2OH in hexane, toluene, Time= 24h, T= 20 °C , Title compound not separated from byproducts Scarpi, Dina; Lo Galbo, Fabrizio; Occhiato, Ernesto G.; Guarna, Antonio; Tetrahedron Asymmetry; vol. 15; nb. 8; (2004); p. 1319 - 1324 View in Reaxys With (1R,2R)-2-(4-methoxycarbonylpiperidin-1-yl)cyclohexanol in hexane, toluene, Time= 24h, T= 20 °C , Title compound not separated from byproducts Gonzalez-Sabin, Javier; Gotor, Vicente; Rebolledo, Francisca; Tetrahedron Asymmetry; vol. 15; nb. 8; (2004); p. 1335 1341 View in Reaxys With titanium(IV) isopropylate, Ti(BINOL)2 in hexane, dichloromethane, Time= 19h, T= 0 °C , Title compound not separated from byproducts Harada, Toshiro; Hiraoka, Yuki; Kusukawa, Takahiro; Marutani, Yasuhisa; Matsui, Shinichiro; Nakatsugawa, Masashi; Kanda, Koso; Organic Letters; vol. 5; nb. 26; (2003); p. 5059 - 5062 View in Reaxys With chiral ferrocenyl-substituted oxazoline ligand in hexane, toluene, Time= 24h, T= 20 °C , Title compound not separated from byproducts Jones, Geraint; Richards, Christopher J.; Tetrahedron Asymmetry; vol. 15; nb. 4; (2004); p. 653 - 664 View in Reaxys With chiral ferrocene catalyst in toluene, Time= 12h, T= 0 °C , Title compound not separated from byproducts Rudolph, Jens; Hermanns, Nina; Bolm, Carsten; Journal of Organic Chemistry; vol. 69; nb. 11; (2004); p. 3997 - 4000 View in Reaxys With (R)-BINOL-supported micelle-derived polymer, titanium(IV) isopropylate in dichloromethane, Time= 10h, T= -10 °C , Title compound not separated from byproducts Takizawa, Shinobu; Patil, Mahesh L.; Yonezawa, Fumiko; Marubayashi, Kazuyoshi; Tanaka, Hiroyuki; Kawai, Tomoji; Sasai, Hiroaki; Tetrahedron Letters; vol. 46; nb. 7; (2005); p. 1193 - 1197 View in Reaxys With titanium(IV) isopropylate, (2S,2'S)-bis(1-hydroxy-1H-perfluorooctyl)biphenyl, Product distribution, Further Variations: Catalysts Omote, Masaaki; Nishimura, Yuji; Sato, Kazuyuki; Ando, Akira; Kumadaki, Itsumaro; Tetrahedron Letters; vol. 46; nb. 2; (2005); p. 319 - 322 View in Reaxys With (1S,4R,2'R)4'-(2-py)spiro[menthane-2,2'-benz[e][1,3]oxazine] in toluene, Time= 48h, T= 0 °C , Product distribution, Further Variations: Reagents, Temperatures Thienthong, Neeranat; Perlmutter, Patrick; Journal of Organometallic Chemistry; vol. 690; nb. 8 SPEC. ISS.; (2005); p. 2027 - 2034 View in Reaxys With polystyrene-supported (R)-2-piperazino-1,1,2-(Ph)3-ethanol in toluene, Time= 4h, T= 0 °C , Product distribution, Thermodynamic data, Further Variations: Reagents, Temperatures, reaction times Castellnou, David; Sola, Lluis; Jimeno, Ciril; Fraile, Jose M.; Mayoral, Jose A.; Riera, Antoni; Pericas, Miquel A.; Journal of Organic Chemistry; vol. 70; nb. 2; (2005); p. 433 - 438 View in Reaxys With (2S)-1-ferrocenylmethylaziridin-2-yl(diphenyl)-methanol in hexane, toluene, T= 0 - 20 °C Wang, Min-Can; Liu, Lan-Tao; Zhang, Jun-Song; Shi, Yan-Yan; Wang, De-Kun; Tetrahedron Asymmetry; vol. 15; nb. 24; (2004); p. 3853 - 3859 View in Reaxys

62/258

2018-07-03 17:29:03

With chiral binaphthol-based titanium(IV) in dichloromethane, Time= 19h Harada, Toshiro; Kanda, Kousou; Hiraoka, Yuuki; Marutani, Yasuhisa; Nakatsugawa, Masashi; Tetrahedron Asymmetry; vol. 15; nb. 24; (2004); p. 3879 - 3883 View in Reaxys With (1S)-1-[2-(dimethylamino)ethyl]-3,3-diMe-norbornan-2-endo-ol in toluene, T= 20 °C , Title compound not separated from byproducts Martinez, Antonio Garcia; Vilar, Enrique Teso; Fraile, Amelia Garcia; De La Moya Cerero, Santiago; Maroto, Beatriz Lora; Tetrahedron; vol. 61; nb. 12; (2005); p. 3055 - 3064 View in Reaxys With (1S)-1-[2-(dimethylamino)ethyl]-7,7-diMe-norbornan-2-exo-ol in toluene, T= 20 °C , Title compound not separated from byproducts Martinez, Antonio Garcia; Vilar, Enrique Teso; Fraile, Amelia Garcia; De La Moya Cerero, Santiago; Maroto, Beatriz Lora; Tetrahedron; vol. 61; nb. 12; (2005); p. 3055 - 3064 View in Reaxys With (1S,3S)-1-(2,2-dimethylpropyl)-3-(1-methyl-1-hydroxyethyl)-2-methyl-1,2,3,4-tetrahydro-η-carboline in toluene, T= 20 °C , Product distribution, Further Variations: Catalysts, Temperatures Zhu; Jiang; Saebo; Pittman Jr.; Journal of Organic Chemistry; vol. 70; nb. 1; (2005); p. 261 - 267 View in Reaxys With (1S,2S,Rp)-2-[MeCH(OH)]-1,1'-[1-(Me2N)propanediyl]ferrocene in toluene, T= 20 °C , Title compound not separated from byproducts Faux, Nadege; Razafimahefa, Dorothee; Picart-Goetgheluck, Sophie; Brocard, Jacques; Tetrahedron Asymmetry; vol. 16; nb. 6; (2005); p. 1189 - 1197 View in Reaxys With N,N'-bis[(1S)-2-hydroxy-1,1,2-triphenylethyl]ethanediamide in hexane, dichloromethane, Time= 24h, T= 0 °C , Title compound not separated from byproducts Blay, Gonzalo; Fernandez, Isabel; Marco-Aleixandre, Alicia; Pedro, Jose R.; Tetrahedron Asymmetry; vol. 16; nb. 6; (2005); p. 1207 - 1213 View in Reaxys With (1R,2R)-pseudoephedrine based ligand in hexane, toluene, T= 25 °C , Title compound not separated from byproducts Sibi, Mukund P.; Stanley, Levi M.; Tetrahedron Asymmetry; vol. 15; nb. 21; (2004); p. 3353 - 3356 View in Reaxys With titanium(IV) isopropylate, (R)-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-7,7'-diol in hexane, dichloromethane, Time= 12h, T= 0 °C , Product distribution, Further Variations: Reagents, Solvents, Temperatures Li, Zhian; Liang, Xinmiao; Wan, Boshun; Wu, Fan; Synthesis; nb. 17; (2004); p. 2805 - 2808 View in Reaxys With chiral [2.2]paracyclophane-4,7-quinone derivative in toluene, Time= 14h, T= 20 °C , Product distribution, Further Variations: Reagents Vorontsova, Natalia; Vorontsov, Evgenii; Antonov, Dmitrii; Starikova, Zoya; Butin, Kim; Braese, Stefan; Hoefener, Sebastian; Rozenberg, Valeria; Advanced Synthesis and Catalysis; vol. 347; nb. 1; (2005); p. 129 - 135 View in Reaxys With (R)-1-[2-(2-pyridyl)phenyl]ethanol in hexane, toluene, Time= 24h, T= 20 °C , Title compound not separated from byproducts Kourist, Robert; Gonzalez-Sabin, Javier; Liz, Ramon; Rebolledo, Francisca; Advanced Synthesis and Catalysis; vol. 347; nb. 5; (2005); p. 695 - 702 View in Reaxys

63/258

2018-07-03 17:29:03

With (R)-(-)-1-(1'-isoquinolinyl)-2-naphthalenemethanol in toluene, Time= 20h, T= 20 °C , Title compound not separated from byproducts Baker, Robert W.; Rea, Simon O.; Sargent, Melvyn V.; Schenkelaars, Elisabeth M.C.; Tjahjandarie, Tjitjik Srie; Totaro, Angela; Tetrahedron; vol. 61; nb. 15; (2005); p. 3733 - 3743 View in Reaxys Stage 1: With (2S)-2-amino-N-(2-aminoethyl)-3-methylbutanamide in hexane, Time= 0.166667h, T= 25 °C Stage 2: in hexane, Time= 18h, T= 0 °C , Title compound not separated from byproducts Sprout, Christopher M.; Richmond, Meaghan L.; Seto, Christopher T.; Journal of Organic Chemistry; vol. 69; nb. 20; (2004); p. 6666 - 6673 View in Reaxys With 6,6'-bis[(R)-2,2'-diOH-1,1'-binaphthyl-3-yl]-2,2'-bipyridyl in hexane, toluene, Time= 24h, T= 22 °C , Title compound not separated from byproducts Bai, Xiao-Li; Kang, Chuan-Qing; Liu, Xu-Dong; Gao, Lian-Xun; Tetrahedron Asymmetry; vol. 16; nb. 3; (2005); p. 727 731 View in Reaxys With (1R,2R)-N,N'-bis((3S,4S)-4-hydroxycyclohexyl)-trans-1,2-diaminocyclohexane in toluene, Time= 16h, T= -30 °C , Title compound not separated from byproducts Cobb, Alexander J.A.; Marson, Charles M.; Tetrahedron; vol. 61; nb. 5; (2005); p. 1269 - 1279 View in Reaxys With (1R,2R)-N,N'-dimethyl-N,N'-bis((3S,4S)-4-hydroxycyclohexyl)-trans-1,2-diaminocyclohexane in toluene, Time= 16h, T= -30 - 20 °C , Title compound not separated from byproducts Cobb, Alexander J.A.; Marson, Charles M.; Tetrahedron; vol. 61; nb. 5; (2005); p. 1269 - 1279 View in Reaxys With 1-((dimethylamino)methyl)-7,7-dimethylbicyclo[2.2.1]heptan-2-ol in hexane, Time= 3h, T= 20 °C , Product distribution, Further Variations: Reagents, Solvents, time Hari, Yoshiyuki; Aoyama, Toyohiko; Synthesis; nb. 4; (2005); p. 583 - 587; Art.No: F15404SS View in Reaxys With (R,R')-bis[2-(N-Bn-methylamino)-3-methoxypropyl]disulfide in hexane, Time= 48h, T= 0 °C , Product distribution, Further Variations: Temperatures, time Braga, Antonio L.; Alves, Elenilson F.; Silveira, Claudio C.; Zeni, Gilson; Appelt, Helmoz R.; Wessjohann, Ludger A.; Synthesis; nb. 4; (2005); p. 588 - 594; Art.No: M04404SS View in Reaxys With chiral salen-based zinc in toluene, Kinetics Fennie, Michael W.; DiMauro, Erin F.; O'Brien, Erin M.; Annamalai, Venkatachalam; Kozlowski, Marisa C.; Tetrahedron; vol. 61; nb. 26; (2005); p. 6249 - 6265 View in Reaxys With chiral salen-based zinc in toluene, Time= 12h, T= -30 °C , Title compound not separated from byproducts Fennie, Michael W.; DiMauro, Erin F.; O'Brien, Erin M.; Annamalai, Venkatachalam; Kozlowski, Marisa C.; Tetrahedron; vol. 61; nb. 26; (2005); p. 6249 - 6265 View in Reaxys With titanium(IV) isopropylate, chiral bis(sulfonamide) ligand in hexane, toluene, T= -45 °C , Title compound not separated from byproducts Costa, Anna M.; Garcia, Celina; Carroll, Patrick J.; Walsh, Patrick J.; Tetrahedron; vol. 61; nb. 26; (2005); p. 6442 - 6446 View in Reaxys With (1R,2S)-2,3-dimethyl-1-phenyl-6-tosyl-3,6-diazahexan-1-ol in hexane, Time= 24h, T= 20 °C , Product distribution, Further Variations: Catalysts

64/258

2018-07-03 17:29:03

Mao, Jincheng; Wan, Boshun; Wang, Rongliang; Wu, Fan; Lu, Shiwei; Journal of Organic Chemistry; vol. 69; nb. 26; (2004); p. 9123 - 9127 View in Reaxys With (R,R)-1,2-Ph2-N,N'-bis(mesitylmethylidene)ethane-1,2-diamine, (R)-3,3'-dibromo-1,1'-bi-2-naphthol in toluene, Time= 24h, T= -20 °C , Title compound not separated from byproducts Du, Haifeng; Zhang, Xue; Wang, Zheng; Ding, Kuiling; Tetrahedron; vol. 61; nb. 40; (2005); p. 9465 - 9477 View in Reaxys With titanium(IV) isopropylate, chiral catalyst in toluene, Time= 12h, T= 20 °C , Title compound not separated from byproducts Wu, Chuan-De; Hu, Aiguo; Zhang, Lin; Lin, Wenbin; Journal of the American Chemical Society; vol. 127; nb. 25; (2005); p. 8940 - 8941 View in Reaxys Stage 1: With (4S,5S)-3,4-dimethyl-5-phenyl-1,3-oxazolidine in toluene, Time= 1h, T= 20 °C Stage 2: in toluene, Time= 48h, Title compound not separated from byproducts Hajji, Chakib; Testa, M. Luisa; Zaballos-Garcia, Elena; Sepulveda-Arques, Jose; Journal of Chemical Research; nb. 7; (2005); p. 420 - 421 View in Reaxys Stage 1: With n-butyllithium, (S)-N-methyl-η,η-(p-C6F17C6H4)2-prolinol in hexane, Time= 0.5h, T= 40 °C Stage 2: in hexane, T= 40 °C , Title compound not separated from byproducts Park, Jin Kyoon; Lee, Hong Geun; Bolm, Carsten; Kim, B. Moon; Chemistry - A European Journal; vol. 11; nb. 3; (2005); p. 945 - 950 View in Reaxys With (2S)-N-benzyl-prolinol thioacetate in hexane, toluene, Time= 65h, T= 0 °C , Product distribution, Further Variations: Reagents Eriksen, Heidi S.; Oyaga, Sandra Cotes; Sherrington, David C.; Gibson, Colin L.; Synlett; nb. 8; (2005); p. 1235 - 1238; Art.No: D04005ST View in Reaxys With (-)-sparteine in hexane, Time= 1h, T= 20 °C , Product distribution, Further Variations: Solvents, Temperatures, reaction times Johansson, Anna; Wingstrand, Erica; Hakansson, Mikael; Journal of Organometallic Chemistry; vol. 690; nb. 16; (2005); p. 3846 - 3853 View in Reaxys With (Ra)-3,3'-bis(diphenylphosphinoyl)-BINOL in tetrahydrofuran, toluene, Time= 3h, T= 20 °C , Product distribution, Further Variations: Reagents, Temperatures Hatano, Manabu; Miyamoto, Takashi; Ishihara, Kazuaki; Advanced Synthesis and Catalysis; vol. 347; nb. 11-13; (2005); p. 1561 - 1568 View in Reaxys With (R)-3-[4,6-bis(dimethylamino)-1,3,5-triazin-2-yl]-1,1'-bi-2-naphthol, titanium(IV) isopropylate in toluene, Time= 5h, T= 0 °C , Title compound not separated from byproducts Guo, Qun-Sheng; Liu, Bing; Lu, Yong-Na; Jiang, Fu-Yong; Song, Hai-Bin; Li, Jin-Shan; Tetrahedron Asymmetry; vol. 16; nb. 22; (2005); p. 3667 - 3671 View in Reaxys With titanium(IV) isopropylate, (S)-(binaphthalen-6-yl)-3H-imidazol-1-ium based ionic liquid in dichloromethane, Time= 18h, T= 20 °C Gadenne, Benoit; Hesemann, Peter; Moreau, Joel J.E.; Tetrahedron Asymmetry; vol. 16; nb. 11; (2005); p. 2001 - 2006 View in Reaxys With (2S,3R)-2-((CH3)2NCH2)-3-(HOCH2)-bicyclo[2.2.1]hept-5-ene in hexane, Time= 48h, T= 0 °C

65/258

2018-07-03 17:29:03

Tanyeli, Cihangir; Suenbuel, Murat; Tetrahedron Asymmetry; vol. 16; nb. 11; (2005); p. 2039 - 2043 View in Reaxys Stage 1: With (S)-3-methoxymethyl-1,1'-bi-2-naphthol, titanium(IV) isopropylate in toluene, T= 20 °C Stage 2: in toluene, Time= 5h, T= 0 °C Guo, Qun-Sheng; Lu, Yong-Na; Liu, Bing; Xiao, Jian; Li, Jin-Shan; Journal of Organometallic Chemistry; vol. 691; nb. 6; (2006); p. 1282 - 1287 View in Reaxys With (1R,5R,6R)-C15H19NO2 in hexane, toluene, T= 0 °C , Product distribution, Further Variations: Reagents, Temperatures Zhong, Yu-Wu; Jiang, Chang-Sheng; Xu, Ming-Hua; Lin, Guo-Qiang; Tetrahedron; vol. 60; nb. 40; (2004); p. 8861 - 8868 View in Reaxys Stage 1: With (3R,5R)-1-N-benzyl-3,5-dihydroxy-piperidine in toluene, Time= 0.5h, T= 0 °C Stage 2: in toluene, Time= 24h, T= 20 °C , Title compound not separated from byproducts Roudeau, Remi; Gomez Pardo, Domingo; Cossy, Janine; Tetrahedron; vol. 62; nb. 10; (2006); p. 2388 - 2394 View in Reaxys With (1S,2R)-norephedrine-based ligand in hexane, toluene, Time= 16h, T= 0 - 20 °C , Title compound not separated from byproducts Unaleroglu, Canan; Aydin, A. Ebru; Demir, Ayhan S.; Tetrahedron Asymmetry; vol. 17; nb. 5; (2006); p. 742 - 749 View in Reaxys With (1R,2S)-norephedrine-based ligand in toluene, T= 0 - 20 °C , Title compound not separated from byproducts Unaleroglu, Canan; Aydin, A. Ebru; Demir, Ayhan S.; Tetrahedron Asymmetry; vol. 17; nb. 5; (2006); p. 742 - 749 View in Reaxys Stage 1: With (1R,2R,3S,5R)(2-Me2N-2,6,6-Me3-bicyclo[3.1.1]hept-3-yl)CH2OH in hexane, Time= 25h, T= 20 °C Stage 2: in hexane, toluene, Time= 20h, T= 20 °C , Title compound not separated from byproducts Szakonyi, Zsolt; Balazs, Arpad; Martinek, Tamas A.; Fueloep, Ferenc; Tetrahedron Asymmetry; vol. 17; nb. 2; (2006); p. 199 - 204 View in Reaxys With (S)-3-(hydroxydiphenylmethyl)morpholine, n-butyllithium in hexane, toluene, Time= 48h, T= 20 °C , Title compound not separated from byproducts Dave, Rajesh; Sasaki, N. Andre; Tetrahedron Asymmetry; vol. 17; nb. 3; (2006); p. 388 - 401 View in Reaxys With (S)-N-benzyl-3-(hydroxydiphenylmethyl)morpholine, n-butyllithium in hexane, toluene, Time= 48h, T= 20 °C , Title compound not separated from byproducts Dave, Rajesh; Sasaki, N. Andre; Tetrahedron Asymmetry; vol. 17; nb. 3; (2006); p. 388 - 401 View in Reaxys With (1'R,1''R,2'R,2''R)-N,N'-bis-[2-(morpholin-4-yl)cyclohexyl]pyridine-2,6-dicarboxamide in hexane, toluene, Time= 16h, T= 20 °C , Title compound not separated from byproducts Gonzalez-Sabin, Javier; Gotor, Vicente; Rebolledo, Francisca; Tetrahedron Asymmetry; vol. 17; nb. 3; (2006); p. 449 - 454 View in Reaxys With (S)-3,3'-bis[bis(η-naphthyl)hydroxymethyl]-1,1'-binaphth-2,2'-diol in toluene, Time= 12h, T= 0 °C , Title compound not separated from byproducts Zhang, Yi-Li; Fan, Qing-Hua; Journal of Chemical Research; nb. 12; (2005); p. 778 - 779 View in Reaxys With titanium(IV) isopropylate, Ti(R,R)bis[Ph2(OH)C]3Me-1,3dioxolan2-yl-C6H4-pCH2CH2-PEfiber in toluene, Time= 24h, T= 0 °C , Product distribution, Further Variations: Reagents Degni, Sylvestre; Wilen, Carl-Eric; Leino, Reko; Organic Letters; vol. 3; nb. 16; (2001); p. 2551 - 2554

66/258

2018-07-03 17:29:03

View in Reaxys With substituted 1,1'-trichalcogena[3]ferrocenophane in hexane, toluene, Time= 18h, T= 0 °C , Product distribution, Further Variations: Reagents, Solvents Fukuzawa, Shin-Ichi; Wachi, Daisuke; Heteroatom Chemistry; vol. 17; nb. 2; (2006); p. 118 - 124 View in Reaxys With (S)-[(4)-4-t-butyl-4,5-dihydrooxazol-2-yl](phenyl)methanol in toluene, Time= 20h, T= 20 °C , Title compound not separated from byproducts Li, Zhi-Ting; Li, Xin-Sheng; Li, Liang-Chao; Xu, Dong-Cheng; Russian Journal of Organic Chemistry; vol. 42; nb. 4; (2006); p. 545 - 549 View in Reaxys With titanium(IV) isopropylate, (S)-Mandelic acid in dichloromethane, toluene, Time= 18h, T= 22 °C , Product distribution, Further Variations: Reagents, Solvents, Temperatures, time Bauer, Tomasz; Gajewiak, Joanna; Tetrahedron; vol. 60; nb. 41; (2004); p. 9163 - 9170 View in Reaxys With (+)-(1R,2R,4R)-7-syn-dimethylaminonorbornan-2-exo-ol in hexane, Time= 1h, T= 20 °C , Product distribution, Further Variations: Reagents De Oliveira, Luciane F.; Costa, Valentim E.U.; Tetrahedron Asymmetry; vol. 15; nb. 16; (2004); p. 2583 - 2590 View in Reaxys Stage 1: With (3aS,7aS)-3-N-[(S)-η-phenylethyl]-octahydrobenzo[d]oxazole in toluene, Time= 0.166667h, T= 20 °C Stage 2: in toluene, Time= 20h, T= 20 °C , Title compound not separated from byproducts Mastranzo, Virginia M.; Santacruz, Ericka; Huelgas, Gabriela; Paz, Evelyn; Sosa-Rivadeneyra, Martha V.; Bernes, Sylvain; Juaristi, Eusebio; Quintero, Leticia; de Parrodi, Cecilia Anaya; Tetrahedron Asymmetry; vol. 17; nb. 11; (2006); p. 1663 - 1670 View in Reaxys With (-)-2-exo-N,N-diethylamino-7-syn-hydroxy-norbornane in hexane, toluene, Time= 15h, T= 20 °C , Product distribution, Further Variations: Reagents, reaction times Martins, Jose E.D.; Mehlecke, Clarissa M.; Gamba, Muriell; Costa, Valentim E.U.; Tetrahedron Asymmetry; vol. 17; nb. 12; (2006); p. 1817 - 1823 View in Reaxys With titanium(IV) isopropylate, (S,S)-3-(1,1'-bi-2-naphthol-3-yl)-5,6,7,8-H4-BINOL in toluene, Time= 5h, T= 0 °C , Product distribution, Further Variations: Reagents Lu, Yong-Na; Guo, Qun-Sheng; Jiang, Fu-Yong; Li, Jin-Shan; Tetrahedron Asymmetry; vol. 17; nb. 12; (2006); p. 1842 1845 View in Reaxys With chiral bridged resorcinarene in toluene, Time= 16h, T= -20 - 20 °C , Product distribution, Further Variations: Reagents Arnott, Gareth; Hunter, Roger; Tetrahedron; vol. 62; nb. 5; (2006); p. 992 - 1000 View in Reaxys Stage 1: With titanium(IV) isopropylate, N,N'-bis[(1S)-2-hydroxy-1-phenylethyl]ethanediamide in toluene, Time= 1h, T= 20 °C Stage 2: in toluene, T= -20 °C , Title compound not separated from byproducts Testa, Maria Luisa; Antista, Licia; Mingoia, Francesco; Zaballos-Garcia, Elena; Journal of Chemical Research; nb. 3; (2006); p. 182 - 184 View in Reaxys Stage 1: With titanium(IV) isopropylate, N,N'-bis-[(1S,2S)-2-OH-1-CH2OH-2-(pNO2Ph)ethyl]ethanediamide in toluene, Time= 1h, T= 20 °C Stage 2: in toluene, T= -20 °C , Title compound not separated from byproducts

67/258

2018-07-03 17:29:03

Testa, Maria Luisa; Antista, Licia; Mingoia, Francesco; Zaballos-Garcia, Elena; Journal of Chemical Research; nb. 3; (2006); p. 182 - 184 View in Reaxys With (Sp,S)-5-[C6H11-CH(Me)-N=C(Me)]-4-OH-[2.2]paracyclophane in hexane, toluene, Time= 12h, T= 0 °C , Product distribution, Further Variations: Reagents Lauterwasser, Frank; Nieger, Martin; Mansikkamaeki, Heidi; Naettinen, Kalle; Braese, Stefan; Chemistry - A European Journal; vol. 11; nb. 15; (2005); p. 4509 - 4525 View in Reaxys With Bis(2-hydroxyphenyl)methane, (S)-Ti(OR)4 [OR=(S)-OCHEt(pTol)] in hexane, dichloromethane, T= -20 °C , Product distribution, Further Variations: Reagents Davis; Balsells; Carroll; Walsh; Organic letters; vol. 3; nb. 14; (2001); p. 2161 - 2164 View in Reaxys With (-)-1-(2-methyl-1,2,3,4-tetrahydroisoquinolin-1-yl)naphthalen-2-ol in n-heptane, toluene, Time= 72h, T= 0 °C MacLeod, Patricia D.; Li, Zhiping; Feng, Jianqing; Li, Chao-Jun; Tetrahedron Letters; vol. 47; nb. 38; (2006); p. 6791 6794 View in Reaxys With titanium(IV) isopropylate, (S)-6-monobrmo-1,1’-bi-2-nahthol in hexane, toluene, Time= 7h, T= 0 °C , Title compound not separated from byproducts Pathak, Kavita; Bhatt, Achyut P.; Abdi, Sayed H.R.; Kureshy, Rukhsana I.; Khan, Noor-ul H.; Ahmad, Irshad; Jasra, Raksh V.; Tetrahedron Asymmetry; vol. 17; nb. 10; (2006); p. 1506 - 1513 View in Reaxys With (S)-3-[(1H-1,2,4-triazol-1-yl)-methyl]-BINOL, titanium(IV) isopropylate in hexane, toluene, T= 0 °C , Title compound not separated from byproducts Liu, Bing; Jiang, Fu-Yong; Song, Hai-Bin; Li, Jin-Shan; Tetrahedron Asymmetry; vol. 17; nb. 14; (2006); p. 2149 - 2153 View in Reaxys With (R)-3-(3,5-diphenylphenyl)-2,2'-dihydroxy-1,1'-binaphthyl, titanium(IV) isopropylate in dichloromethane, Time= 1h, T= 0 °C , Product distribution, Further Variations: Reagents, Temperatures, reaction times Harada, Toshiro; Kanda, Kousou; Organic Letters; vol. 8; nb. 17; (2006); p. 3817 - 3819 View in Reaxys With 2-[(R)-N-Me-pyrrolidin-2-yl]-(1R)-ferrocenyldiphenylmethanol in hexane, toluene, Time= 48h, T= 0 °C , Title compound not separated from byproducts Ahern, Theresa; Mueller-Bunz, Helge; Guiry, Patrick J.; Journal of Organic Chemistry; vol. 71; nb. 20; (2006); p. 7596 7602 View in Reaxys With 2-[(R)-N-Me-pyrrolidin-2-yl]-(1S)-ferrocenyldiphenylmethanol in hexane, toluene, Time= 48h, T= 0 °C , Title compound not separated from byproducts Ahern, Theresa; Mueller-Bunz, Helge; Guiry, Patrick J.; Journal of Organic Chemistry; vol. 71; nb. 20; (2006); p. 7596 7602 View in Reaxys With (1R,2R)-1-(cis-2,6-Me2-piperidin-1-yl)-3-MeO-1-Ph-propan-2-ol in hexane, toluene, T= 0 °C , Kinetics, Further Variations: Reagents Jimeno, Ciril; Vidal-Ferran, Anton; Pericas, Miquel A.; Organic Letters; vol. 8; nb. 18; (2006); p. 3895 - 3898 View in Reaxys With (S,S)-chiral hydroxyalkyl oxazoline in hexane, benzene, Time= 18h, T= 20 °C , Product distribution, Further Variations: ligands Bauer, Michael; Kazmaier, Uli; Journal of Organometallic Chemistry; vol. 691; nb. 10; (2006); p. 2155 - 2158

68/258

2018-07-03 17:29:03

View in Reaxys With chiral imine in hexane, toluene, Time= 24h, T= 20 °C , Title compound not separated from byproducts Mino, Takashi; Suzuki, Atsushi; Yamashita, Masakazu; Narita, Shusaku; Shirae, Yoshiaki; Sakamoto, Masami; Fujita, Tsutomu; Journal of Organometallic Chemistry; vol. 691; nb. 20; (2006); p. 4297 - 4303 View in Reaxys With chiral [2.2]paracyclophane-based N,O-ligand in hexane, toluene, Time= 18h, T= 0 - 20 °C , Title compound not separated from byproducts Sugiyama, Shigeo; Aoki, Yoshinori; Ishii, Keitaro; Tetrahedron Asymmetry; vol. 17; nb. 20; (2006); p. 2847 - 2856 View in Reaxys With (+)-[{2-(2,4-(MeO)2C6H3)-1-CON(iPr)2C5H3}Fe{CON(iPr)2C5H4}] in toluene, Time= 10h, T= 20 °C , Title compound not separated from byproducts Laufer, Radoslaw; Veith, Ulrich; Taylor, Nicholas J.; Snieckus, Victor; Canadian Journal of Chemistry; vol. 84; nb. 2; (2006); p. 356 - 369 View in Reaxys With (S,E)-2-((2-(2,2,2-trifluoro-1-hydroxyethyl)-phenylimino)methyl)phenol in hexane, T= 0 °C , Product distribution, Further Variations: Catalysts, Solvents Sokeirik, Yasser Samir; Omote, Masaaki; Sato, Kazuyuki; Kumadaki, Itsumaro; Ando, Akira; Tetrahedron Asymmetry; vol. 17; nb. 18; (2006); p. 2654 - 2658 View in Reaxys Stage 1: With titanium(IV) isopropylate, tris-BINOL-[Ti(Oi-Pr)2]3 in hexane, toluene, T= 0 °C Stage 2: in hexane, toluene, Time= 20h, T= 0 °C , Title compound not separated from byproducts Harada, Toshiro; Nakatsugawa, Masashi; Synlett; nb. 2; (2006); p. 321 - 323 View in Reaxys With chiral C2-symmetric ferrocenyl aziridino alcohol in hexane, toluene, Time= 48h, T= 0 - 20 °C , Product distribution, Further Variations: Catalysts, Temperatures Wang, Min-Can; Hou, Xue-Hui; Xu, Cui-Lian; Liu, Lan-Tao; Li, Gui-Lan; Wang, De-Kun; Synthesis; nb. 20; (2005); p. 3620 - 3626; Art.No: F09705SS View in Reaxys With potassium tert-butylate, chiral imidazolinium salt in hexane, toluene, Time= 30h, T= 20 °C , Title compound not separated from byproducts Jurcik, Vaclav; Gilani, Mazhar; Wilhelm, Rene; European Journal of Organic Chemistry; nb. 22; (2006); p. 5103 - 5109 View in Reaxys Stage 1: With substituted (P,R,S)-tetrabenzoxazine in hexane, toluene, Time= 0.5h, T= -78 °C Stage 2: in hexane, toluene, Time= 12h, T= -78 - 20 °C , Title compound not separated from byproducts Buckley, Benjamin R.; Boxhall, Jonathan Y.; Bulman Page, Philip C.; Chan, Yohan; Elsegood, Mark R. J.; Heaney, Harry; Holmes, Kathryn E.; McIldowie, Matthew J.; McKee, Vickie; McGrath, Matthew J.; Mocerino, Mauro; Poulton, Andrew M.; Sampler, Edward P.; Skelton, Brian W.; White, Allan H.; European Journal of Organic Chemistry; nb. 22; (2006); p. 5117 - 5134 View in Reaxys With chiral oxazoline with ferrocene backbone in toluene, Time= 8h, T= 0 °C , Product distribution, Further Variations: Reagents, Solvents, Temperatures, Reaction time Hua, Genghong; Liu, Delong; Xie, Fang; Zhang, Wanbin; Tetrahedron Letters; vol. 48; nb. 3; (2007); p. 385 - 388 View in Reaxys With (+)-(S,4Rp,13Sp)-4-OH-13-(4-tBu-oxazolin-2-yl)[2.2]paracy.. in toluene, Time= 4h, Title compound not separated from byproducts Bolm, Carsten; Whelligan, Daniel K.; Advanced Synthesis and Catalysis; vol. 348; nb. 15; (2006); p. 2093 - 2100

69/258

2018-07-03 17:29:03

View in Reaxys With (-)-(S,4Sp,5Rp)-4-OH-5-(4-iPr-oxazolin-2-yl)[2.2]paracycl.. in toluene, Time= 24h, Title compound not separated from byproducts Bolm, Carsten; Whelligan, Daniel K.; Advanced Synthesis and Catalysis; vol. 348; nb. 15; (2006); p. 2093 - 2100 View in Reaxys With (R)-3,3'-diformyl-2,2'-binaphthol bis-N-(dimethylamino)imine in hexane, toluene, Time= 6h, T= -20 °C , Title compound not separated from byproducts Arai, Takayoshi; Endo, Yoko; Yanagisawa, Akira; Tetrahedron Asymmetry; vol. 18; nb. 2; (2007); p. 165 - 169 View in Reaxys Stage 1: With (-)-3,3'-di(2,5-Me2-C6H3)CH2-2,2'-di-OH-1,1'-binaphtalene in toluene, Time= 0.5h, T= 20 °C Stage 2: in toluene, Time= 24h, T= 20 °C , Title compound not separated from byproducts Zhang, Yi-Li; Zhang, Feng; Tang, Wei-Jun; Wu, Qing-Lai; Fan, Qing-Hua; Synlett; nb. 8; (2006); p. 1250 - 1254 View in Reaxys With L-tyrosine-functionalized dendrimeric copolymer in toluene, Time= 8h, T= 0 °C , Title compound not separated from byproducts. Bosman, Anton W.; Vestberg, Robert; Heumann, Andi; Frechet, Jean M. J.; Hawker, Craig J.; Journal of the American Chemical Society; vol. 125; nb. 3; (2003); p. 715 - 728 View in Reaxys With polymeric chiral norbornene-2-endo,3-endo dicarboxylate in toluene, Time= 48h, T= 0 °C , Product distribution, Further Variations: Catalysts Bolm, Carsten; Tanyeli, Cihangir; Grenz, Achim; Dinter, Christian L.; Advanced Synthesis and Catalysis; vol. 344; nb. 6-7; (2002); p. 649 - 656 View in Reaxys With (R)-2-(4-HOCH2C6H4)-1,2-Ph2-2-C5H10N-1-yl-ethanol on resin in toluene, Time= 4h, T= 0 °C , Product distribution, Kinetics, Further Variations: Catalysts, Temperatures Pericas, Miquel A.; Castellnou, David; Rodriguez, Israel; Riera, Antoni; Sola, Lluis; Advanced Synthesis and Catalysis; vol. 345; nb. 12; (2003); p. 1305 - 1313 View in Reaxys With (S)-2-tBu-6-[(E)-(2-OH-1,1,2-Ph3-ethyl)NH]CH-4-MeO-phenol, titanium(IV) isopropylate in toluene, T= -20 - -10 °C , Product distribution, Further Variations: Reagents, Temperatures Braun, Manfred; Fleischer, Ralf; Mai, Brigitte; Schneider, Marc-Andre; Lachenicht, Stefan; Advanced Synthesis and Catalysis; vol. 346; nb. 4; (2004); p. 474 - 482 View in Reaxys With trimethylsilylsubstituted fenchyl alcohol in hexane, Time= 24h, T= -30 °C , Alkylation, Product distribution, Further Variations: Reagents Goldfuss, Bernd; Steigelmann, Melanie; Rominger, Frank; European Journal of Organic Chemistry; nb. 9; (2000); p. 1785 1792 View in Reaxys With (1S,2R)-1-[(diethylamino)methyl]-3,3-dimethylnorbornan-2-ol in hexane, T= 20 °C , Title compound not separated from byproducts. Martinez, Antonio Garcia; Vilar, Enrique Teso; Fraile, Amelia Garcia; de la Moya Cerero, Santiago; Martinez Ruiz, Paloma; Diaz Morillo, Cristina; Tetrahedron Asymmetry; vol. 18; nb. 6; (2007); p. 742 - 749 View in Reaxys Stage 1: With chiral (ferrocenyl)(2-aziridinyl)methanol-based catalyst in hexane, toluene, Time= 0.5h, T= 20 °C Stage 2: in hexane, toluene, Time= 10h, T= 20 °C , Further stages. Title compound not separated from byproducts.

70/258

2018-07-03 17:29:03

Bulut, Adnan; Aslan, Ayhan; Izgue, Enver Cagri; Dogan, Oezdemir; Tetrahedron Asymmetry; vol. 18; nb. 8; (2007); p. 1013 - 1016 View in Reaxys With (R)-3,3'-bis-[(Me2N)2P(=O)-]-BINOL in tetrahydrofuran, toluene, Time= 4h, T= 50 °C , Product distribution, Further Variations: Reagents, Temperatures, time Hatano, Manabu; Miyamoto, Takashi; Ishihara, Kazuaki; Synlett; nb. 11; (2006); p. 1762 - 1764 View in Reaxys With 1(R)-C(Ph2)OH-2,2-Me2-3(S)-Me2NCH2-cyclopropane in hexane, Time= 48h, T= -15 °C , Product distribution, Further Variations: Temperatures, Solvents, Reagents, Time Zhong, Jiangchun; Wang, Mingan; Guo, Hongchao; Yin, Mingming; Bian, QingHua; Wang, Min; Synlett; nb. 11; (2006); p. 1667 - 1670 View in Reaxys With (S)-2-(1-amino-2,2-dimethylpropyl)-4,6-di-tert-butylphenol in hexane, toluene, Time= 22h, T= 0 °C Yang, Xiao-Feng; Wang, Zhao-Hui; Koshizawa, Tomoaki; Yasutake, Mikio; Zhang, Guang-You; Hirose, Takuji; Tetrahedron Asymmetry; vol. 18; nb. 10; (2007); p. 1257 - 1263 View in Reaxys With (R)-2-(1-amino-2,2-dimethylpropyl)-4,6-di-tert-butylphenol in hexane, toluene, Time= 22h, T= 20 °C Yang, Xiao-Feng; Wang, Zhao-Hui; Koshizawa, Tomoaki; Yasutake, Mikio; Zhang, Guang-You; Hirose, Takuji; Tetrahedron Asymmetry; vol. 18; nb. 10; (2007); p. 1257 - 1263 View in Reaxys With polymer-supported chiral aziridine-based reagent in toluene, T= 0 - 20 °C , Title compound not separated from byproducts. Page, Philip C. Bulman; Allin, Steven M.; Dilly, Suzanne J.; Buckley, Benjamin R.; Synthetic Communications; vol. 37; nb. 12; (2007); p. 2019 - 2030 View in Reaxys With titanium(IV) isopropylate, 1,1'-bi-2-naphthol in hexane, dichloromethane, Time= 10h, T= -10 °C , Title compound not separated from byproducts. Takizawa, Shinobu; Patil, Mahesh L.; Marubayashi, Kazuyoshi; Sasai, Hiroaki; Tetrahedron; vol. 63; nb. 28; (2007); p. 6512 - 6528 View in Reaxys With titanium(IV) isopropylate in hexane, dichloromethane, Time= 7h, T= -10 °C , Title compound not separated from byproducts. Takizawa, Shinobu; Patil, Mahesh L.; Marubayashi, Kazuyoshi; Sasai, Hiroaki; Tetrahedron; vol. 63; nb. 28; (2007); p. 6512 - 6528 View in Reaxys With titanium(IV) isopropylate in hexane, dichloromethane, Time= 7h, T= 0 °C , Product distribution, Further Variations: Solvents, Reagents Yin, Liang; Li, Rong; Wang, Fushan; Wang, Huanling; Zheng, Yunfeng; Wang, Chaofeng; Ma, Jiantai; Tetrahedron Asymmetry; vol. 18; nb. 11; (2007); p. 1383 - 1389 View in Reaxys With chiral ethylzinc fluoroalkylarenethiolate in hexane, Time= 6h, T= 20 °C , Product distribution, Further Variations: Catalysts Kleijn, Henk; Rijnberg, Evelien; Jastrzebski, Johann T. B. H.; Van Koten, Gerard; Organic Letters; vol. 1; nb. 6; (1999); p. 853 - 855 View in Reaxys With titanium(IV) isopropylate in hexane, toluene, Time= 3h, T= -78 - -30 °C , Product distribution, Further Variations: Reagents

71/258

2018-07-03 17:29:03

Omote, Masaaki; Nishimura, Yuji; Sato, Kazuyuki; Ando, Akira; Kumadaki, Itsumaro; Journal of Fluorine Chemistry; vol. 127; nb. 7; (2006); p. 977 - 979 View in Reaxys With chiral oxazoline derivative in toluene, T= -20 °C , Title compound not separated from byproducts. Seebach, Dieter; Pichota, Arkadius; Beck, Albert K.; Pinkerton, Anthony B.; Litz, Thomas; Karjalainen, Jaana; Gramlich, Volker; Organic Letters; vol. 1; nb. 1; (1999); p. 55 - 58 View in Reaxys With ((2R,3S)-3-(2-NH2C6H4NHCH2)-bicyclo[2.2.1]heptan-2-yl)CH2OH in hexane, toluene, Time= 48h, T= 0 °C , Product distribution, Further Variations: Solvents, Temperatures, Reagents Tanyeli, Cihangir; Odabas, Serhat; Erdem, Mine; Cakir, Esen; Keskin, Eda; Tetrahedron Asymmetry; vol. 18; nb. 19; (2007); p. 2349 - 2357 View in Reaxys With titanium(IV) isopropylate in hexane, toluene, Time= 5h, T= 0 °C , Product distribution, Further Variations: Reagents, Solvents, Temperatures Li, Ma; Jin, Rin-Zhe; Lue, Guang-Hua; Bian, Zhen; Ding, Meng-Xian; Gao, Lian-Xun; Synthesis; nb. 16; (2007); p. 2461 2470 View in Reaxys With chiral polymer-supported N-picolylvalinol-based catalyst in toluene, Time= 4h, T= 20 °C , Title compound not separated from byproducts. Kelsen, Vinciane; Pierrat, Philippe; Gros, Philippe C.; Tetrahedron; vol. 63; nb. 43; (2007); p. 10693 - 10697 View in Reaxys With titanium(IV) isopropylate in hexane, toluene, Time= 5h, T= 20 °C , Product distribution, Further Variations: Reagents Jiang, Fu-Yong; Liu, Bing; Dong, Zhi-Bing; Li, Jin-Shan; Journal of Organometallic Chemistry; vol. 692; nb. 20; (2007); p. 4377 - 4380 View in Reaxys With PS-4-BnO(CH2)4O-[(3R,5S)-5-(CPh2OH)-1-methylpyrrolidin-3-yl] in hexane, Time= 36h, T= 20 °C , Title compound not separated from byproducts. Wang, Su-Xi; Chen, Fen-Er; Chemical and Pharmaceutical Bulletin; vol. 55; nb. 7; (2007); p. 1011 - 1013 View in Reaxys With (S)-N-(3-Me-1-(1-pyrrolidinyl)butan-2-yl)-NH-P(O)Ph2 in toluene, Time= 12h, T= 0 °C , Title compound not separated from byproducts. Hatano, Manabu; Miyamoto, Takashi; Ishihara, Kazuaki; Organic Letters; vol. 9; nb. 22; (2007); p. 4535 - 4538 View in Reaxys With titanium(IV) isopropylate, chiral binaphthol-based cadmium complex in toluene, Time= 15h, T= 20 °C , Title compound not separated from byproducts. Wu, Chuan-De; Lin, Wenbin; Angewandte Chemie - International Edition; vol. 46; nb. 7; (2007); p. 1075 - 1078 View in Reaxys With titanium(IV) isopropylate in toluene, Time= 5h, T= 20 °C Dong, Zhi-Bing; Liu, Bing; Fang, Cao; Li, Jin-Shan; Journal of Organometallic Chemistry; vol. 693; nb. 1; (2008); p. 17 - 22 View in Reaxys With titanium(IV) isopropylate in toluene, T= -20 °C , Product distribution, Further Variations: Reagents Satyanarayana, Tummanapalli; Kagan, Henri B.; Chemistry - A European Journal; vol. 12; nb. 22; (2006); p. 5785 - 5789 View in Reaxys With [(2S,3S)-2-amino-3-perfluorooctyl-propan-3-ol]-based ligand in hexane, toluene, Time= 6h, T= 0 - 20 °C , Title compound not separated from byproducts.

72/258

2018-07-03 17:29:03

Omote, Masaaki; Eto, Yusuke; Tarui, Atsushi; Sato, Kazuyuki; Ando, Akira; Tetrahedron Asymmetry; vol. 18; nb. 23; (2007); p. 2768 - 2772 View in Reaxys With [(2S,3R)-2-amino-3-perfluorobutyl-propan-3-ol]-based ligand in hexane, toluene, Time= 6h, T= 0 - 20 °C , Title compound not separated from byproducts. Omote, Masaaki; Eto, Yusuke; Tarui, Atsushi; Sato, Kazuyuki; Ando, Akira; Tetrahedron Asymmetry; vol. 18; nb. 23; (2007); p. 2768 - 2772 View in Reaxys 1-Phenylpropan-1-ol. Diethylzinc (1 M in heptane; 1 m L) was introduced into a Schlenk under a nitrogen atmosphere. Toluene (0.5 mL), ligand 7a (0.04 mmol in 0.5 mL toluene) and benzaldehyde (0.5 mmol) were subsequently added. The reaction mixture was stirred at room temperature over a period of 24 hours, cooled to O0C and subsequently quenched with an aqueous HCI solution (2M, 5 mL). The reaction mixture was washed with diethyl ether (3 x 5 mL), followed by washing with a saturated aqueous sodium chloride solution. The organic layer was dried using anhydrous magnesium sulfate and filtered. Upon removal of the solvent, the product was isolated by means of thin layer chromatography (hexane/ethyl acetate, 5:1). The fraction having an Rf of 0.37 was collected. The fraction was subsequently extracted with chloroform to yield the product as a yellow oil. HPLC (Daicel Chiralcel OD- H, hexane/isopropanol = 97.5:2.5, flow rate = 0.5 mL/min): tR = 25.1 min, tR = 28.3 min, ee=60percent; 1H

NMR (CDCI3, 300 MHz, ppm): η 7.34-7.20 (m, 5H), 4.54 (t, J = 6.0 Hz, 1 H), 2.54 (brs, 1 H), 1.86-1.64 (m, 2H), 0.88 (t, J =

6.0 Hz, 3H). Stage 1: in toluene, Time= 24h, T= 20 °C Stage 2: With hydrogenchloride, water in toluene Patent; LI, Chao-Jun; WO2007/98608; (2007); (A1) English View in Reaxys With (1R,2S)-2-(benzylamino)-1-phenyl-1-propanol in hexane, toluene, Time= 24h, T= 20 °C , Product distribution, Further Variations: Reagents Parrott II, Raleigh W.; Hitchcock, Shawn R.; Tetrahedron Asymmetry; vol. 19; nb. 1; (2008); p. 19 - 26 View in Reaxys With (S)-2-(dibutylamino)-1-(furan-2-yl)ethanol in hexane, Time= 5h, T= 0 °C , Product distribution, Further Variations: Reagents, Solvents, Temperatures Paolucci, Claudio; Rosini, Goffredo; Tetrahedron Asymmetry; vol. 18; nb. 24; (2007); p. 2923 - 2946 View in Reaxys With (1S,4S)-2,5-dimethyl-2,5-diazabicyclo[2.2.1]heptane in hexane, toluene, Time= 20h, T= 0 °C , Product distribution, Further Variations: Reagents, Temperatures, concentration; time Melgar-Fernandez, Roberto; Gonzalez-Olvera, Rodrigo; Olivares-Romero, J. Luis; Gonzalez-Lopez, Vianney; RomeroPonce, Leticia; Ramirez-Zarate, Maria Del Refugio; Demare, Patricia; Regla, Ignacio; Juaristi, Eusebio; European Journal of Organic Chemistry; nb. 4; (2008); p. 655 - 672 View in Reaxys With chiral bicyclo[3.1.1]heptane-2,3-diol-based reagent in hexane, T= 20 °C , Title compound not separated from byproducts. Szakonyi, Zsolt; Hetenyi, Anasztazia; Fueloep, Ferenc; Tetrahedron; vol. 64; nb. 6; (2008); p. 1034 - 1039 View in Reaxys With (1R,2S)-ephedrine-end-functionalized polystyrene in toluene, Time= 48h, T= 0 °C , Title compound not separated from byproducts. El-Shehawy, Ashraf A.; Sugiyama, Kenji; Hirao, Akira; Tetrahedron Asymmetry; vol. 19; nb. 4; (2008); p. 425 - 434 View in Reaxys With (1S,2R)-ephedrine-end-functionalized polystyrene in toluene, Time= 48h, T= 0 °C , Title compound not separated from byproducts. El-Shehawy, Ashraf A.; Sugiyama, Kenji; Hirao, Akira; Tetrahedron Asymmetry; vol. 19; nb. 4; (2008); p. 425 - 434 View in Reaxys

73/258

2018-07-03 17:29:03

With N-Me-1-[(R)-Ph-(1R)-(1-naphthyl)ethylaminomethyl]-2-naphthol in toluene, Time= 24h, T= 20 °C , Title compound not separated from byproducts. Szatmari, Istvan; Sillanpaeae, Reijo; Fueloep, Ferenc; Tetrahedron Asymmetry; vol. 19; nb. 5; (2008); p. 612 - 617 View in Reaxys With Ni*[(S)-2-amino-N-(4-methoxybenzyl)-3-phenyl-propionamide] in toluene, Time= 18h, T= 20 °C , Title compound not separated from byproducts. Burguete, M. Isabel; Collado, Manuel; Escorihuela, Jorge; Luis, Santiago V.; Angewandte Chemie - International Edition; vol. 46; nb. 47; (2007); p. 9002 - 9005 View in Reaxys With Ni*2[(S)-2-amino-N-(4-methoxybenzyl)-3-phenyl-propionamide] in toluene, Time= 18h, T= 20 °C , Title compound not separated from byproducts. Burguete, M. Isabel; Collado, Manuel; Escorihuela, Jorge; Luis, Santiago V.; Angewandte Chemie - International Edition; vol. 46; nb. 47; (2007); p. 9002 - 9005 View in Reaxys With 2-hydroxy-1-naphthaldehyde (-)-ephedrine-derived hydrazone in hexane, toluene, Time= 24h, T= 25 °C , Title compound not separated from byproducts. Parrott II, Raleigh W.; Dore, Delvis D.; Chandrashekar, Seshanand P.; Bentley, Jeromy T.; Morgan, Brittany S.; Hitchcock, Shawn R.; Tetrahedron Asymmetry; vol. 19; nb. 5; (2008); p. 607 - 611 View in Reaxys With n-butyllithium in toluene, Time= 20h, T= 5 °C , Title compound not separated from byproducts. Hernandez-Rodriguez, Marcos; Avila-Ortiz, Claudia Gabriela; Del Campo, Jorge M.; Hernandez-Romero, Delia; Rosales-Hoz, Maria J.; Juaristi, Eusebio; Australian Journal of Chemistry; vol. 61; nb. 5; (2008); p. 364 - 375 View in Reaxys With chiral BINOL-based Ti complex in hexane, toluene, Time= 1h, T= 20 °C Taniguchi, Tomohiro; Fukuba, Taka-Aki; Nakatsuka, Shuhei; Hayase, Shuichi; Kawatsura, Motoi; Uno, Hidemitsu; Itoh, Toshiyuki; Journal of Organic Chemistry; vol. 73; nb. 10; (2008); p. 3875 - 3884 View in Reaxys With chiral camphor-based tertiary-amido alcohol in hexane, Time= 5h, T= 20 °C , Title compound not separated from byproducts. de las Casas Engel, Tomas; Lora Maroto, Beatriz; Garcia Martinez, Antonio; de la Moya Cerero, Santiago; Tetrahedron Asymmetry; vol. 19; nb. 6; (2008); p. 646 - 650 View in Reaxys Stage 1: With (S)-1,1,1-trifluoro-3-piperidinopropan-2-ol in hexane, Time= 0.166667h, T= 20 °C Stage 2: in hexane, Time= 48h, T= 0 - 20 °C , Further stages. Title compound not separated from byproducts. Harada, Akinori; Fujiwara, Yasuyuki; Katagiri, Toshimasa; Tetrahedron Asymmetry; vol. 19; nb. 10; (2008); p. 1210 - 1214 View in Reaxys With (1R,2R)-N-(2-C6H12N-1,2-Ph2-C2H2)-4-Me-PhSO2NH in toluene, Time= 24h, T= 20 °C Martins, Jose E.D.; Wills, Martin; Tetrahedron Asymmetry; vol. 19; nb. 10; (2008); p. 1250 - 1255 View in Reaxys With (1S,2S)-N-(2-C5H10N-1,2-Ph2-C2H2)-4-Me-PhSO2NH in toluene, Time= 24h, T= 20 °C Martins, Jose E.D.; Wills, Martin; Tetrahedron Asymmetry; vol. 19; nb. 10; (2008); p. 1250 - 1255 View in Reaxys With chiral N,N-bis(2-hydroxybenzyl)amine-derived ligand in dichloromethane, Time= 14h, T= 20 °C , Product distribution, Further Variations: Reagents, Solvents, Temperatures Yang, Xiao-Feng; Hirose, Takuji; Zhang, Guang-You; Tetrahedron Asymmetry; vol. 19; nb. 14; (2008); p. 1670 - 1675

74/258

2018-07-03 17:29:03

View in Reaxys With (1R,2R,4S,6S)-2-(2-HO-C6H4-)bicyclo[2.2.2]octane-2,6-diol in diethyl ether, hexane, Time= 40h, T= 0 °C , Title compound not separated from byproducts. Olsson, Cecilia; Friberg, Annika; Frejd, Torbjoern; Tetrahedron Asymmetry; vol. 19; nb. 12; (2008); p. 1475 - 1482 View in Reaxys With (1R,2R,4S,6S)-2-(2-MeO-C6H4-)bicyclo[2.2.2]octane-2,6-diol in diethyl ether, hexane, Time= 40h, T= 0 °C , Product distribution, Further Variations: Reagents Olsson, Cecilia; Friberg, Annika; Frejd, Torbjoern; Tetrahedron Asymmetry; vol. 19; nb. 12; (2008); p. 1475 - 1482 View in Reaxys With chiral bicyclo[2.2.1]heptan-2-ol-derived catalyst in tetrahydrofuran, hexane, Time= 48h, T= 20 °C , Product distribution, Further Variations: Reagents Olsson, Cecilia; Helgesson, Sara; Frejd, Torbjoern; Tetrahedron Asymmetry; vol. 19; nb. 12; (2008); p. 1483 - 1492 View in Reaxys Stage 1: With (R)-2-(2'-piperidinyl)pyridine in diethyl ether, hexane, Time= 0.5h, T= 0 - 20 °C Stage 2: in diethyl ether, hexane, Time= 20h, Further stages. Title compound not separated from byproducts. Cheng, Yan-Qin; Bian, Zheng; Kang, Chuan-Qing; Guo, Hai-Quan; Gao, Lian-Xun; Tetrahedron Asymmetry; vol. 19; nb. 13; (2008); p. 1572 - 1575 View in Reaxys Stage 1: With chiral cyclohexyl(amino)methylferrocene-based catalyst in hexane, toluene, Time= 0.5h Stage 2: in hexane, toluene, Time= 24h, T= 20 °C , Further stages. Title compound not separated from byproducts. Grach, Guillaume; Reboul, Vincent; Metzner, Patrick; Tetrahedron Asymmetry; vol. 19; nb. 14; (2008); p. 1744 - 1750 View in Reaxys With oxycodone in hexane, toluene, Time= 40h, T= -30 °C , Title compound not separated from byproducts. Dabiri, Minoo; Salehi, Peyman; Kozehgary, Gholamreza; Heydari, Seddigheh; Heydari, Akbar; Esfandyari, Maryam; Tetrahedron Asymmetry; vol. 19; nb. 16; (2008); p. 1970 - 1972 View in Reaxys With chiral 2-(C(OH)Ph2)-1-(pyrrolidin-2-yl)methylpyrrolidine in toluene, Time= 72h, T= 20 °C , Product distribution, Further Variations: Reagents Fu; Ding; Wang; Tao; Synthetic Communications; vol. 38; nb. 15; (2008); p. 2672 - 2683 View in Reaxys With (1R,2R,4R)-2-OH-1-piperidinomethyl-7,7-Me2-norbornane in hexane, Time= 5h, T= 20 °C , Product distribution, Further Variations: Reagents de las Casas Engel, Tomas; Maroto, Beatriz Lora; Martinez, Antonio Garcia; de la Moya Cerero, Santiago; Tetrahedron Asymmetry; vol. 19; nb. 17; (2008); p. 2003 - 2006 View in Reaxys With chiral diphenyl sulfoxide-derived aminoalcohol in benzene, T= 0 - 20 °C , Product distribution, Further Variations: Reagents Rachwalski, Michal; Kwiatkowska, Malgorzata; Drabowicz, Jozef; Klos, Marcin; Wieczorek, Wanda M.; Szyrej, Malgorzata; Sieron, Leslaw; Kielbasinski, Piotr; Tetrahedron Asymmetry; vol. 19; nb. 17; (2008); p. 2096 - 2101 View in Reaxys With titanium(IV) isopropylate, (R,R)-hydroxybenzoin in diethyl ether, hexane, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Dean, Melissa A.; Hitchcock, Shawn R.; Tetrahedron Asymmetry; vol. 19; nb. 22; (2008); p. 2563 - 2567 View in Reaxys With (R,R)-hydroxybenzoin in diethyl ether, hexane, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction

75/258

2018-07-03 17:29:03

Dean, Melissa A.; Hitchcock, Shawn R.; Tetrahedron Asymmetry; vol. 19; nb. 22; (2008); p. 2563 - 2567 View in Reaxys With (Rp)-12-[(2,6-dimethylphenylimino)methyl][2.2]paracyclophan-4-ol in toluene, Time= 0 - 20h, optical yield given as percent ee, enantioselective reaction Antonov, Dmitrii Yu.; Rozenberg, Valeria I.; Danilova, Tat'yana I.; Starikova, Zoya A.; Hopf, Henning; European Journal of Organic Chemistry; nb. 6; (2008); p. 1038 - 1048 View in Reaxys With titanium(IV) isopropylate, C34H24N2O8 in hexane, dichloromethane, Time= 5h, T= 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Gou, Shaohua; Judeh, Zaher M.A.; Tetrahedron Letters; vol. 50; nb. 3; (2009); p. 281 - 283 View in Reaxys With 1,3-bis[(1R,2S)-2-hydroxy-1-methyl-2-phenylethyl]-4,5-imidazolinium tetrafluoroborate, potassium tert-butylate, copper(II) bis(trifluoromethanesulfonate) in hexane, toluene, Time= 46h, T= 20 °C , optical yield given as percent ee Gilani, Mazhar; Wilhelm, Rene; Tetrahedron Asymmetry; vol. 19; nb. 20; (2008); p. 2346 - 2352 View in Reaxys Stage 1: With C23H34N2O4S in hexane, T= 0 °C , Inert atmosphere Stage 2: in hexane, Time= 24h, T= 0 °C , Inert atmosphere Stage 3: With hydrogenchloride, water in hexane, Inert atmosphere, optical yield given as percent ee, enantioselective reaction Sun, Jiangtao; Pan, Xu; Dai, Zhenya; Zhu, Chengjian; Tetrahedron Asymmetry; vol. 19; nb. 21; (2008); p. 2451 - 2457 View in Reaxys Stage 1: With titanium(IV) isopropylate, (1S,12S)-N-benzyl-15,15-dimethyl-3-azatetracyclo[10.2.1.0(2,11).0(4,9)]pentadeca-2(11),3,5,7,9-pentaen-1-ylmethanesulfonamide in toluene, Time= 16h, T= -10 °C , Inert atmosphere Stage 2: With water, ammonium chloride in methanol, toluene, optical yield given as percent ee, enantioselective reaction Martinez, Ricardo; Zoli, Luca; Cozzi, Pier Giorgio; Ramon, Diego J.; Yus, Miguel; Tetrahedron Asymmetry; vol. 19; nb. 22; (2008); p. 2600 - 2607 View in Reaxys With (R,Sp,R)-4,15-dihydroxy-5,16-[di-1-(1-phenylethylimino)ethyl][2.2]paracyclophane in toluene, T= 0 - 20 °C , Inert atmosphere, optical yield given as percent ee Vorontsova, Natalia V.; Rozenberg, Valeria I.; Sergeeva, Elena V.; Vorontsov, Evgenii V.; Starikova, Zoya A.; Lyssenko, Konstantin A.; Hopf, Henning; Chemistry - A European Journal; vol. 14; nb. 15; (2008); p. 4600 - 4617 View in Reaxys With (Sp,R)-4,15-dihydroxy-5-[1-(1-phenylethylimino)ethyl][2.2]paracyclophane in toluene, T= 0 - 20 °C , Inert atmosphere, optical yield given as percent ee Vorontsova, Natalia V.; Rozenberg, Valeria I.; Sergeeva, Elena V.; Vorontsov, Evgenii V.; Starikova, Zoya A.; Lyssenko, Konstantin A.; Hopf, Henning; Chemistry - A European Journal; vol. 14; nb. 15; (2008); p. 4600 - 4617 View in Reaxys With (10,10-dimethyl-5-pyridin-4-yl-6-aza-tricyclo[7.1.1.0(2,7)]-undeca-2(7),3,5-trien-8-yl)-diphenyl-methanol in hexane, toluene, Time= 5h, T= 20 °C , Inert atmosphere, optical yield given as percent ee Chang, Tien-Chu; Chen, Chinpiao; Journal of the Chinese Chemical Society; vol. 55; nb. 3; (2008); p. 606 - 615 View in Reaxys Stage 1: With C11H21NOS in hexane, toluene, Time= 0.5h, T= 20 °C Stage 2: in hexane, toluene, Time= 22h, T= 20 °C Stage 3: With hydrogenchloride, water in hexane, toluene, Time= 0.166667h Bauer, Michael; Maurer, Frauke; Hoffmann, Svenja M.; Kazmaier, Uli; Synlett; nb. 20; (2008); p. 3202 - 3207 View in Reaxys Stage 1: With (1S,2R,3S,5S)-6,6-dimethyl-3-piperidinobicyclo[3.1.1]heptan-2-ol, (1R,2S,3R,5R)-6,6-dimethyl-3-piperidinobicyclo[3.1.1]heptan-2-ol in hexane, Time= 18h, T= 0 °C , Inert atmosphere

76/258

2018-07-03 17:29:03

Stage 2: With water, ammonium chloride in hexane, T= 0 °C Binder, Caitlin M.; Bautista, April; Zaidlewicz, Marek; Krzeminski, Marek P.; Oliver, Allen; Singaram, Bakthan; Journal of Organic Chemistry; vol. 74; nb. 6; (2009); p. 2337 - 2343 View in Reaxys Stage 1: With (+)-methyl [(2S,3R,S(S))-4-methyl-2-(1-naphthylsulfonylamino)-3-(p-tolylsulfinylamino)]pentanoate in hexane, dichloromethane, Time= 0.166667h, T= 20 °C Stage 2: With titanium(IV) isopropylate in hexane, dichloromethane, Time= 0.5h, T= 20 °C Stage 3:optical yield given as percent eeenantioselective reactionFurther stages Viso, Alma; Fernandez de la Pradilla, Roberto; Urena, Mercedes; Tetrahedron; vol. 65; nb. 18; (2009); p. 3757 - 3766 View in Reaxys Stage 1: With (-)-methyl [(2R,3S,S(S))-4-methyl-3-(2-methoxynaphthylsulfinylamino)-2-(1-naphthylsulfonylamino)]pentanoate in hexane, dichloromethane, Time= 0.166667h, T= 20 °C Stage 2: With titanium(IV) isopropylate in hexane, dichloromethane, Time= 0.5h, T= 20 °C Stage 3:optical yield given as percent eeenantioselective reactionFurther stages Viso, Alma; Fernandez de la Pradilla, Roberto; Urena, Mercedes; Tetrahedron; vol. 65; nb. 18; (2009); p. 3757 - 3766 View in Reaxys Stage 1: With (1S,5S,7R)-(3-(2,2,2-trifluoroethyl)-6,8-dioxa-3-azabicyclo[3.2.1]oct-7-yl)methanol in hexane, toluene, Time= 0.5h Stage 2: in hexane, toluene, Time= 18h, T= 20 °C Stage 3: With hydrogenchloride, water in hexane, toluene, optical yield given as percent ee Scarpi, Dina; Occhiato, Ernesto G.; Guarna, Antonio; Tetrahedron Asymmetry; vol. 20; nb. 3; (2009); p. 340 - 350 View in Reaxys Stage 1: With (1S,2R)-2-piperidine-1-indanol in hexane, toluene, Time= 0.333333h, T= 20 °C , Inert atmosphere Stage 2: in hexane, toluene, T= 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Rodriguez-Escrich, Sergi; Sola, Lluis; Jimeno, Ciril; Rodriguez-Escrich, Carles; Pericas, Miquel A.; Advanced Synthesis and Catalysis; vol. 350; nb. 14-15; (2008); p. 2250 - 2260 View in Reaxys Stage 1: With (1S,2S)-1-dimethylamino-2-indanol in hexane, toluene, Time= 0.333333h, T= 20 °C , Inert atmosphere Stage 2: in hexane, toluene, T= 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Rodriguez-Escrich, Sergi; Sola, Lluis; Jimeno, Ciril; Rodriguez-Escrich, Carles; Pericas, Miquel A.; Advanced Synthesis and Catalysis; vol. 350; nb. 14-15; (2008); p. 2250 - 2260 View in Reaxys Stage 1: With (1S,2R,4R)-7,7-dimethyl-1-morpholin-4-yl-bicyclo[2.2.1]heptan-2-ol in hexane, Time= 12h, T= 25 °C Stage 2: With ammonium chloride in hexane, water, optical yield given as percent ee, enantioselective reaction Wu, Zhi-Long; Wu, Hsyueh-Liang; Wu, Ping-Yu; Uang, Biing-Jiun; Tetrahedron Asymmetry; vol. 20; nb. 13; (2009); p. 1556 - 1560 View in Reaxys Stage 1: With (S,pR)-2-[(2-diphenylhydroxymethyl)ferrocenyl]-4-isopropyloxazoline in hexane, toluene, Time= 0.5h, T= 25 °C Stage 2: in hexane, toluene, T= 0 °C , Inert atmosphere Stage 3: With hydrogenchloride in hexane, water, toluene, optical yield given as percent ee Garabatos-Perera, Jose Ramon; Butenschoen, Holger; Journal of Organometallic Chemistry; vol. 694; nb. 13; (2009); p. 2047 - 2052 View in Reaxys With (S)-3-phenyl-2-(piperidin-1-yl)-propan-1-ol in hexane, toluene, Time= 40h, T= -30 °C , optical yield given as percent ee Salehi, Peyman; Dabiri, Minoo; Kozehgary, Gholamreza; Heydari, Seddigheh; Synthetic Communications; vol. 39; nb. 14; (2009); p. 2575 - 2584 View in Reaxys With (R)-2-(piperidin-1-yl)butan-1-ol in hexane, toluene, Time= 40h, T= 10 °C , optical yield given as percent ee

77/258

2018-07-03 17:29:03

Salehi, Peyman; Dabiri, Minoo; Kozehgary, Gholamreza; Heydari, Seddigheh; Synthetic Communications; vol. 39; nb. 14; (2009); p. 2575 - 2584 View in Reaxys Stage 1: With C29H30N2O3S in hexane, toluene, Time= 24.5h, T= 0 - 10 °C , Inert atmosphere Stage 2: With hydrogenchloride, water in hexane, toluene, T= 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Mao, Jincheng; Synthetic Communications; vol. 39; nb. 20; (2009); p. 3710 - 3721 View in Reaxys Stage 1: With N-((1S,2R)-1-hydroxy-1-phenylpropan-2-yl)furan-2-carboxamide in hexane, toluene, T= 0 °C Stage 2: With hydrogenchloride, water in hexane, toluene, enantioselective reaction Ananthi, Nallamuthu; Balakrishnan, Umesh; Vinu, Ajayan; Ariga, Katsuhiko; Velmathi, Sivan; Tetrahedron Asymmetry; vol. 20; nb. 15; (2009); p. 1731 - 1735 View in Reaxys Stage 1: With N-(2-[(4S)-4-tert-butyl-4,5-dihydro-1,3-oxazol-2-yl]phenyl)pyridin-2-amine in toluene, T= 0 - 20 °C Stage 2: in toluene, Time= 24h, T= -20 °C , optical yield given as percent ee Coeffard, Vincent; Mueller-Bunz, Helge; Guiry, Patrick J.; Organic and Biomolecular Chemistry; vol. 7; nb. 8; (2009); p. 1723 - 1734 View in Reaxys Stage 1: With N-{2-[(4S)-4-tert-butyl-4,5-dihydro-1,3-oxazol-2-yl]phenyl}-6-(trifluoromethyl)pyridin-2-amine in toluene, T= 0 - 20 °C Stage 2: in toluene, Time= 24h, T= -20 °C , optical yield given as percent ee Coeffard, Vincent; Mueller-Bunz, Helge; Guiry, Patrick J.; Organic and Biomolecular Chemistry; vol. 7; nb. 8; (2009); p. 1723 - 1734 View in Reaxys Stage 1: With (R)-(+)-N,N'-bis(3H-isobenzofuran-1-ylidene)-1,1'-binaphthyl-2,2'-diamine in hexane, toluene, Time= 0.333333h, T= 20 °C , Inert atmosphere Stage 2: in hexane, toluene, Time= 24h, T= 20 °C , Inert atmosphere Stage 3: With ammonium chloride in hexane, toluene, Inert atmosphere, optical yield given as percent ee, enantioselective reaction Noel, Timothy; Vandyck, Koen; Robeyns, Koen; Van Meervelt, Luc; Van der Eycken, Johan; Tetrahedron; vol. 65; nb. 43; (2009); p. 8879 - 8884 View in Reaxys Stage 1: With C20H26N4 in hexane, toluene, Time= 0.333333h, T= 20 °C , Inert atmosphere Stage 2: in hexane, toluene, Time= 3h, T= 20 °C , Inert atmosphere Stage 3: With ammonium chloride in hexane, toluene, Inert atmosphere, optical yield given as percent ee, enantioselective reaction Noel, Timothy; Vandyck, Koen; Robeyns, Koen; Van Meervelt, Luc; Van der Eycken, Johan; Tetrahedron; vol. 65; nb. 43; (2009); p. 8879 - 8884 View in Reaxys The phosphoramide compound (L1) and the ligands (L3) to (L12) were used as a ligand. Each of these ligands was added, and benzaldehyde and diethylzinc were reacted to synthesize an optically active secondary alcohol. 3.0 ml (3.0 mmol) of diethylzinc (1.0 M toluene solution) was added to a Schlenk reaction tube containing 0.10 mmol of the phosphoramide compound (L1) or the ligands (L3) to (L12) under a nitrogen atmosphere, and stirred at 0°C for 30 minutes. Then, 1.0 mmol of benzaldehyde was added to the reaction solution and stirred at 0°C for 24 hours. The completion of the reaction was confirmed by a TLC. After confirmation, 10 ml of a saturated aqueous ammonium chloride solution was added and warmed to room temperature. Extraction from the mixture was performed twice using 15 ml of diethyl ether. The extracted organic layer was washed with 10 ml of a saturated sodium chloride aqueous solution, and dried with magnesium sulfate. Then, the filtration was performed using "Celite" (trade name), and the solvent was distilled off under reduced pressure. The obtained concentrated liquid was purified by passing through silica gel column chromatography(pentane/diethyl ether = (10/1) to (2/1)), and thus an optically active secondary alcohol was obtained. The structure of the synthesized optically active secondary alcohol, the reaction time, yield, and enantiomeric excess are indicated together with the structure of each of the above ligands.

78/258

2018-07-03 17:29:03

Stage 1: With C23H27N2OP in toluene, Time= 24.5h, T= 0 °C , Inert atmosphere Stage 2: With ammonium chloride in tolune, water Patent; National University Corporation Nagoya University; Sekisui Medical Co., Ltd.; EP2128167; (2009); (A1) English View in Reaxys 5 :5. Asymmetric diethylzinc addition; To a chilled (0°C) solution of 5 (0.05 g, 0.15 mmol) in toluene (0.75 mL), 1M (solution in hexanes) diethylzinc (1.30 mL, 1.30 mmol) was added dropwise and stirred at room temperature for 0.5h. At 0°C, fresh distilled benzaldehyde (0.06 mL, 0.65 mmol) was added and stirred at 0°C for 2 days. The reaction mixture was quenched with cold saturated NH4C1 (10 mL) and extracted with cold DCM (20 mL and 10 mL). The extracts were combined, dried over anhydrous MgSO4 and concentrated to give crude product (75 percent conversion). The crude product was purified by flash chromatography using EtOAc/hexanes (1:9) to afford a pure adduct. The enantiomeric excess was determined by chiral HPLC (20percent ee): Daicel Chiracel OD-H, /-PrOH/Hexane 2/98, flow rate 1.0 ml/min, fo 15.1 OS)-isomer and 18.3 (^)-isomer, 254 run; .H NMR (300 MHz, CDC13) 8 0.90 (t, 3H), 1.80 (m, 2H), 4.60 (m, 1H), 7.35 (m, 5H).Note : racemic mixture, /R 14.8 and 18.4. Stage 1: With (1S,4R,2'R)-(-)-4'-(2-pyridyl)spiro[menthane-2,2'-benzo[e][1,3]oxazine(2H)] in toluene, Time= 0.5h, T= 20 °C Stage 2: in toluene, Time= 48h, T= 0 °C Stage 3: With water, ammonium chloride in toluene, Product distribution / selectivity Patent; MONASH UNIVERSITY; WO2006/2470; (2006); (A1) English View in Reaxys With C16H20N2O2S2 in hexane, benzene, T= 0 - 20 °C , Inert atmosphere, optical yield given as percent ee Lawecka, Justyna; Bujnicki, Bogdan; Drabowicz, Jozef; Luczak, Jerzy; Rykowski, Andrzej; Phosphorus, Sulfur and Silicon and the Related Elements; vol. 184; nb. 5; (2009); p. 1247 - 1256 View in Reaxys Stage 1: With 2-(2'-hydroxymethylphenyl)-(3aS,8aR)-3a,8a-dihydro-8H-indeno[1,2-d]oxazoline in hexane, toluene, Time= 0.333333h, T= 20 °C Stage 2: in hexane, toluene, Time= 48h, T= 0 °C , Inert atmosphere Stage 3: With water, ammonium chloride in hexane, toluene, Inert atmosphere, optical yield given as percent ee, enantioselective reaction Noel, Timothy; Robeyns, Koen; Meervelt, Luc Van; Eycken, Erik Van der; Eycken, Johan Van der; Tetrahedron Asymmetry; vol. 20; nb. 17; (2009); p. 1962 - 1968 View in Reaxys Stage 1: With (1R,2S)-1-phenyl-2-(N-methyl-N-benzylamino)propan-1-ol in toluene, Inert atmosphere Stage 2: in toluene, Inert atmosphere Stage 3: With ammonium chloride in toluene, Inert atmosphere, optical yield given as percent ee, enantioselective reaction Banerjee, Sucharita; Groeper, Jonathan A.; Standard, Jean M.; Hitchcock, Shawn R.; Tetrahedron Asymmetry; vol. 20; nb. 18; (2009); p. 2154 - 2161 View in Reaxys Stage 1: With (1S,2S)-2-(N-benzyl-N-methylamino)-1-phenyl-1-propanol in toluene, Inert atmosphere Stage 2: in toluene, Inert atmosphere Stage 3: With ammonium chloride in toluene, Inert atmosphere, optical yield given as percent ee, enantioselective reaction Banerjee, Sucharita; Groeper, Jonathan A.; Standard, Jean M.; Hitchcock, Shawn R.; Tetrahedron Asymmetry; vol. 20; nb. 18; (2009); p. 2154 - 2161 View in Reaxys With (1R,2S)-2-(((1,3-dioxolan-2-yl)methyl)(methyl)amino)-1-phenylpropan-1-ol in hexane, toluene, T= 0 - 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Dean, Melissa A.; Hitchcock, Shawn R.; Tetrahedron Asymmetry; vol. 20; nb. 20; (2009); p. 2351 - 2356 View in Reaxys With (1S,2S)-2-(((1,3-dioxolan-2-yl)methyl)(methyl)amino)-1-phenylpropan-1-ol in hexane, toluene, T= 0 - 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Dean, Melissa A.; Hitchcock, Shawn R.; Tetrahedron Asymmetry; vol. 20; nb. 20; (2009); p. 2351 - 2356 View in Reaxys

79/258

2018-07-03 17:29:03

38 %Chromat.

Stage 1: With titanium(IV) isopropylate, N,N'-[(2η-hydroxy)pinan-3-ylidene]ethane-1,2-diamine in hexane, toluene, Time= 0.0833333h Stage 2: in hexane, toluene, Time= 24h, T= -10 °C Stage 3: With ammonium chloride in hexane, water, toluene, optical yield given as percent ee, enantioselective reaction Salehi, Peyman; Dabiri, Minoo; Kozehgary, Gholamreza; Baghbanzadeh, Mostafa; Tetrahedron Asymmetry; vol. 20; nb. 22; (2009); p. 2609 - 2611 View in Reaxys Stage 1: With BF4 (1-)*C14H28NO(1+) in toluene, Time= 0.5h, T= 20 °C , Inert atmosphere Stage 2: in toluene, Time= 20h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Malhotra, Sanjay V.; Wang, Yun; Kumar, Vineet; Letters in Organic Chemistry; vol. 6; nb. 3; (2009); p. 264 - 268 View in Reaxys Stage 1: With benzyl (1S,3R)-3-(dimethylamino)-2,2,3-trimethylcyclopentylcarbamate in hexane, cyclohexane, Time= 6h, T= 0 °C , Inert atmosphere Stage 2: With hydrogenchloride, water, ammonium chloride in hexane, cyclohexane, Inert atmosphere, enantioselective reaction Murtinho, Dina; Elisa Silva Serra; Rocha Gonsalves, A.M.d'A.; Tetrahedron Asymmetry; vol. 21; nb. 1; (2010); p. 62 - 68 View in Reaxys Stage 1: With 7,7-dimethyl-1-morpholin-4-ylmethylbicyclo[2.2.1]heptane-2-ol in hexane, Time= 1h, T= 20 °C , Inert atmosphere Stage 2: in hexane, Time= 5h, T= 20 °C Stage 3: With hydrogenchloride in hexane, water, optical yield given as percent ee, enantioselective reaction Sanchez-Carnerero, Esther Marquez; de las Casas Engel, Tomas; Maroto, Beatriz Lora; de la Moya Cerero, Santiago; Tetrahedron Asymmetry; vol. 20; nb. 23; (2009); p. 2655 - 2657 View in Reaxys Stage 1: With C16H31NO3 in hexane, Time= 1h, T= 20 °C , Inert atmosphere Stage 2: in hexane, Time= 5h, T= 20 °C Stage 3: With hydrogenchloride in hexane, water, optical yield given as percent ee, enantioselective reaction Sanchez-Carnerero, Esther Marquez; de las Casas Engel, Tomas; Maroto, Beatriz Lora; de la Moya Cerero, Santiago; Tetrahedron Asymmetry; vol. 20; nb. 23; (2009); p. 2655 - 2657 View in Reaxys Stage 1: With titanium(IV) isopropylate, (1S,2R,4R)-N-((R)-1-hydroxybutan-2-yl)-2-hydroxy-7,7-dimethylbicyclo[2.2.1]heptane-1-methanesulfonamide, benzoic acid in hexane, toluene, Time= 0.0833333h, T= -20 °C Stage 2: in hexane, toluene, Time= 20h, T= -20 °C Stage 3: With water, ammonium chloride in hexane, toluene, optical yield given as percent ee, enantioselective reaction Dabiri, Minoo; Salehi, Peyman; Heydari, Seddigheh; Kozehgary, Gholamreza; Synthetic Communications; vol. 39; nb. 24; (2009); p. 4350 - 4361 View in Reaxys Stage 1: With (1S,2R,4R)-N-((R)-1-hydroxybutan-2-yl)-2-hydroxy-7,7-dimethylbicyclo[2.2.1]heptane-1-methanesulfonamide in hexane, toluene, Time= 0.0833333h, T= -20 °C Stage 2: in hexane, toluene, Time= 20h, T= -20 °C Stage 3: With water, ammonium chloride in hexane, toluene, optical yield given as percent ee, enantioselective reaction Dabiri, Minoo; Salehi, Peyman; Heydari, Seddigheh; Kozehgary, Gholamreza; Synthetic Communications; vol. 39; nb. 24; (2009); p. 4350 - 4361 View in Reaxys Stage 1: With C18H16N2 in tetrahydrofuran, hexane, Time= 30h, T= 0 °C Stage 2: With water, ammonium chloride in tetrahydrofuran, hexane, Saturated solution, optical yield given as percent ee, enantioselective reaction Qi, Gao; Judeh, Zaher M.A.; Tetrahedron Asymmetry; vol. 21; nb. 4; (2010); p. 429 - 436 View in Reaxys Stage 1: With C18H16N2 in tetrahydrofuran, hexane, T= 0 - 20 °C

80/258

2018-07-03 17:29:03

Stage 2: in tetrahydrofuran, hexane, T= 0 °C , Inert atmosphere Stage 3: With ammonium chloride in tetrahydrofuran, hexane, optical yield given as percent ee, enantioselective reaction Qi, Gao; Ji, Yao Qiong; Judeh, Zaher M.A.; Tetrahedron; vol. 66; nb. 23; (2010); p. 4195 - 4205 View in Reaxys Stage 1: With (-)-MIB in toluene, T= 20 °C , Inert atmosphere Stage 2: With hydrogenchloride, water in toluene, Kinetics, Reagent/catalyst, optical yield given as percent ee Valera, Fernando E.; Quaranta, Michela; Moran, Antonio; Blacker, John; Armstrong, Alan; Cabral, Joao T.; Blackmond, Donna G.; Angewandte Chemie - International Edition; vol. 49; nb. 14; (2010); p. 2478 - 2485 View in Reaxys Stage 1: With 12-bromo-4-hydroxy-5-[1-(1-phenylethylimino)ethyl][2.2]paracyclophane in toluene, T= 0 - 20 °C Stage 2: With water in toluene, Time= 0.166667h, optical yield given as percent ee, enantioselective reaction Vorontsova, Natalia V.; Bystrova, Galina S.; Antonov, Dmitrii Yu.; Vologzhanina, Anna V.; Godovikov, Ivan A.; Il'in, Michail M.; Tetrahedron Asymmetry; vol. 21; nb. 6; (2010); p. 731 - 738 View in Reaxys Stage 1: With (S)-5-[phenyl-(1'-phenylethylimino)methyl]-4-hydroxy[2.2]paracyclophane in toluene, T= 0 - 20 °C Stage 2: With water in toluene, Time= 0.166667h, optical yield given as percent ee, enantioselective reaction Vorontsova, Natalia V.; Bystrova, Galina S.; Antonov, Dmitrii Yu.; Vologzhanina, Anna V.; Godovikov, Ivan A.; Il'in, Michail M.; Tetrahedron Asymmetry; vol. 21; nb. 6; (2010); p. 731 - 738 View in Reaxys With (1S,3S)-2,2-dimethyl-3-(dimethylamino)-1,3-diphenylpropan-1-ol in hexane, toluene, Time= 2h, optical yield given as percent ee, enantioselective reaction Patil; Gonnade; Joshi; Tetrahedron; vol. 66; nb. 27-28; (2010); p. 5036 - 5041 View in Reaxys Stage 1: With titanium(IV) isopropylate, (1R,1''R)-2',2''-(propane-1,3-diylbis(oxy))bis-(5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl) in toluene, Time= 5h, T= 0 °C , Inert atmosphere Stage 2: With hydrogenchloride in water, toluene, Inert atmosphere, optical yield given as percent ee, enantioselective reaction Abreu, Artur R.; Pereira, Mariette M.; Bayon, J. Carles; Tetrahedron; vol. 66; nb. 3; (2010); p. 743 - 749 View in Reaxys Stage 1: With titanium(IV) isopropylate, 2',2''-((4S,5S)-2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene)bis(oxy)di-1,1'-binaphthyl in toluene, Time= 5h, T= 0 °C , Inert atmosphere Stage 2: With hydrogenchloride in water, toluene, optical yield given as percent ee, enantioselective reaction Abreu, Artur R.; Pereira, Mariette M.; Bayon, J. Carles; Tetrahedron; vol. 66; nb. 3; (2010); p. 743 - 749 View in Reaxys Stage 1: With (-)-MIB in toluene, Time= 0.0833333h, T= 20 °C Stage 2: in toluene, Time= 12h, T= 20 °C , optical yield given as percent ee, enantioselective reaction Gastl, Christoph; Laschat, Sabine; Synthesis; nb. 15; (2010); p. 2643 - 2651; Art.No: Z07810SS View in Reaxys Stage 1: With (1R,2S)-2-[(1H-pyrrol-2-yl)methylamino]-1-phenylpropan-1-ol in hexane, toluene, Time= 5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, T= 0 - 20 °C , Inert atmosphere, optical yield given as percent ee Tasgin, Dilek Isik; Unaleroglu, Canan; Applied Organometallic Chemistry; vol. 24; nb. 1; (2010); p. 33 - 37 View in Reaxys With titanium(IV) isopropylate, (1R,1"R)-2',2"-(propane-1,3-diylbis(oxy))bis(5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl-2-ol) in hexane, toluene, Time= 5h, Inert atmosphere, optical yield given as percent ee, enantioselective reaction Abreu, Artur R.; Loureno, Mirtha; Peral, Daniel; Rosado, Mario T.S.; Eusebio, Maria E.S.; Palacios, Scar; Bayon, J. Carles; Pereira, Mariette M.; Journal of Molecular Catalysis A: Chemical; vol. 325; nb. 1-2; (2010); p. 91 - 97 View in Reaxys

81/258

2018-07-03 17:29:03

With titanium(IV) isopropylate, (1S,4S)-(N-benzyl)-(2-keto-7,7-dimethylbicyclo[2.2.1]hept-1-yl)methanesulfonamide in dichloromethane, T= -50 - 20 °C , Inert atmosphere, enantioselective reaction Kozakiewicz, Anna; Ullrich, Malgorzata; Welniak, Miroslaw; Wojtczak, Andrzej; Journal of Molecular Catalysis A: Chemical; vol. 326; nb. 1-2; (2010); p. 128 - 140 View in Reaxys With titanium(IV) isopropylate, (1S,2R,4S)-(N-benzyl)-(2-hydroxy-7,7-dimethylbicyclo[2.2.1]hept-1-yl)methanesulfonamide in dichloromethane, T= -50 - 20 °C , Inert atmosphere, enantioselective reaction Kozakiewicz, Anna; Ullrich, Malgorzata; Welniak, Miroslaw; Wojtczak, Andrzej; Journal of Molecular Catalysis A: Chemical; vol. 326; nb. 1-2; (2010); p. 128 - 140 View in Reaxys Stage 1: With 2-(benzyl(ethyl)amino)-3-ethyl-1-phenylpentan-3-ol in hexane, T= 0 °C , Inert atmosphere Stage 2: in hexane, T= 0 - 20 °C , Inert atmosphere Stage 3: With water, ammonium chloride in hexane, optical yield given as percent ee, enantioselective reaction Zhang, Cong-Hai; Yan, Sheng-Jiao; Pan, Sheng-Qiang; Huang, Rong; Lin, Jun; Bulletin of the Korean Chemical Society; vol. 31; nb. 4; (2010); p. 869 - 873 View in Reaxys Stage 1: With 2-(benzyl(ethyl)amino)-1,1,3-triphenylpropan-1-ol in hexane, T= 0 °C , Inert atmosphere Stage 2: in hexane, T= 0 - 20 °C , Inert atmosphere Stage 3: With water, ammonium chloride in hexane, optical yield given as percent ee Zhang, Cong-Hai; Yan, Sheng-Jiao; Pan, Sheng-Qiang; Huang, Rong; Lin, Jun; Bulletin of the Korean Chemical Society; vol. 31; nb. 4; (2010); p. 869 - 873 View in Reaxys With C24H28N2 Gualandi, Andrea; Manoni, Francesco; Monari, Magda; Savoia, Diego; Tetrahedron; vol. 66; nb. 3; (2010); p. 715 - 720 View in Reaxys With C21H21NO in toluene, Time= 24h, T= 20 °C , optical yield given as percent ee MacLeod, Patricia D.; Reckling, Amy M.; Li, Chao-Jun; Heterocycles; vol. 80; nb. 2; (2010); p. 1319 - 1337 View in Reaxys With (R)-2-((4-dimethylamino)benzylideneamino)butan-1-ol in hexane, toluene, Time= 40h, T= 30 °C , optical yield given as percent ee, enantioselective reaction Salehi; Dabiri; Kozehgary; Journal of the Iranian Chemical Society; vol. 7; nb. 1; (2010); p. 100 - 106 View in Reaxys With (S,E)-2,4-di-tert-butyl-6-((2-(methoxymethyl)pyrrolidin-1-ylimino)methyl)phenol in toluene, Time= 18h, T= 25 °C , optical yield given as percent ee Banerjee, Sucharita; Ferrence, Gregory M.; Hitchcock, Shawn R.; Tetrahedron Asymmetry; vol. 21; nb. 7; (2010); p. 837 845 View in Reaxys Stage 1: With (+)-(1R,2R,4R,6S)-4-(allyloxy)-2-(2-methoxyphenyl)-bicyclo[2.2.2]octane-2,6-diol, (1S,2S,4S,6R)-4-(allyloxy)-2-(2-methoxyphenyl)-bicyclo[2.2.2]octane-2,6-diol in diethyl ether, Time= 0.75h, T= 0 °C Stage 2: in diethyl ether, hexane, Time= 40h, T= 0 °C , enantioselective reaction Manner, Sophie; Hansson, Cecilia; Larsson, Johanna M.; Oltner, Viveca T.; Frejd, Torbjoern; Tetrahedron Asymmetry; vol. 21; nb. 11-12; (2010); p. 1374 - 1381 View in Reaxys Stage 1: With titanium(IV) isopropylate, (2S)-N-[(1S)-2-hydroxy-1-phenyl-ethyl]-5-oxo-pyrrolidine-2-carboxamide in hexane, dichloromethane, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, dichloromethane, Time= 18h, T= 0 - 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction

82/258

2018-07-03 17:29:03

Geoghegan, Paul; O'Leary, Patrick; Tetrahedron Asymmetry; vol. 21; nb. 7; (2010); p. 867 - 870 View in Reaxys Stage 1: With solid phase supported cinchonidine in hexane, toluene, Time= 1h, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, Time= 84h, T= 20 °C , Inert atmosphere, optical yield given as percent ee Ma, Xuebing; Wang, Yonghua; Wang, Wei; Cao, Jun; Catalysis Communications; vol. 11; nb. 5; (2010); p. 401 - 407 View in Reaxys With titanium(IV) isopropylate, C52H38O10 in toluene, Inert atmosphere, enantioselective reaction Ma, Liqing; Falkowski, Joseph M.; Abney, Carter; Lin, Wenbin; Nature Chemistry; vol. 2; nb. 10; (2010); p. 838 - 846 View in Reaxys With (1S,2S)-1-[(diethylamino)methyl]-2,7,7-trimethylnorbornan-2-ol in hexane, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Martinez, Antonio Garcia; Vilar, Enrique Teso; Fraile, Amelia Garcia; De La Moya Cerero, Santiago; Ruiz, Paloma Martinez; Morillo, Cristina Diaz; Chirality; vol. 22; nb. 8; (2010); p. 778 - 787 View in Reaxys With (1S,2S)-1-[(diethylamino)methyl]-2,3,3-trimethylnorbornan-2-ol in hexane, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Martinez, Antonio Garcia; Vilar, Enrique Teso; Fraile, Amelia Garcia; De La Moya Cerero, Santiago; Ruiz, Paloma Martinez; Morillo, Cristina Diaz; Chirality; vol. 22; nb. 8; (2010); p. 778 - 787 View in Reaxys 2 :Example 2: Testing Amino-alcohol Catalysts in the Catalytic Asymmetric Addition of Diethylzinc to Aldehydes. The ligands that "were synthesized and characterized "were screened for use as catalysts in the asymmetric addition of diethylzinc to benzaldehyde. All reactions were run in toluene and kept at 0° C for 24 h (Table 3).General procedure for the catalytic asymmetric addition of diethylzinc to benzaldehyde. To a stirred solution of the catalyst (0.20 equiv) in toluene (2 mL) at 0 0C was added diethylzinc (1.0 M in hexane, 1.08 mL). After stirring the reaction for 30 min at 0 0C. benzaldehyde (0.05 mL. 0.49 mmol) was added and the reaction was stirred at this temperature for 24 h. The reaction was quenched with an aqueous saturated solution of ammonium chloride (2 mL). and the mixture was extracted with diethyl ether (3 x 5 mL). The combined organic layers were dried over MgSO4. filtered, and concentrated to afford the crude product. Purification by RPLC (10percent EtOAc/hexanes) provided the product as a colorless oil. The ee of the alcohol products was determined by chiral HPLC.(i?)-l-Phenyl-l-propanol (17): [η]31 D +37.8 (c 1.70. CH2C12). 95percent ee by HPLC analysis (Chiralcel OD column. 2percent z-propanol/hexanes. 1.00 mL/min. η = 219 nm). Retention times: R (major) 11.98 min. S (minor) 14.95 min.(if)-l-(4-Chlorophenyl)-l-propanol: [η]31 D +31.5 (c 1.90. CH2C12). 94percent ee by HPLC analysis (Chiralcel OD column, 2percent z-propanol/hexanes. 0.80 mL/min. η = 254 nm). Retention times: R (major) 15.04 min, S (minor) 16.41 min.(i?)-l-(4-Methoxyphenyl)-l-propanol: [η]31 D +28.3 (c 0.70. CH2C12). 94percent ee by HPLC analysis (Chiralcel OD column. 2percent z'-propanol/hexanes. 1.00 mL/min. η = 261 nm). Retention times: R (major) 45.09 min. S (minor) 55.69 min.(i?)-l-Phenyl-3-pentanol: [η]31 D -18.6 (c 1.25. CH2C12). 69percent ee by HPLC analysis (Chiralcel OD column. 5percent z'-propanol/hexanes. 1.00 mL/min. η = 262 nm). Retention times: R (major) 9.14 min. S (minor) 12.94 min.(i?)-l-Phenylpent-l-(E)-en-3-ol: [η]31 D -1.0 (c 2.60. CH2C12): 72percent ee by HPLC analysis (Chiralcel OD column eluted with 5percent z'-propanol/hexanes at 0.80 mL/min and detection at η = 254 nm). Retention times: R (major) 14.97 min, S (minor) 24.68 min.15 93 (5)-l,3-Diphenyl-prop-2-yn-l-ol (93). Diethylzinc (1.0 M in hexane, 0.39 mL) was added dropwise to a solution of 75d (1 1 mg, 0.02 mmol) in toluene (2 mL) at room temperature. After 15 h, phenylacetylene (0.06 mL, 0.41 mmol) was added at room temperature and the reaction was stirred for 1 h. Benzaldehyde (0.02 mL, 0.20 mmol) was then added and the reaction was stirred for 24 h at room temperature. The reaction was quenched with water and extracted with diethyl ether (2 x 5 mL). The combined organic layers were dried over magnesium sulfate, filtered, and concentrated. The crude oil was purified by RPLC (10percent EtOAc/hexanes) to afford 93percent (38 mg) of the product as a colorless oil; 13percent ee determined by HPLC analysis (Chiralcel OD column eluted with 20percent /-propanol/hexanes at 1.00 mL/min and detection at η = 254 nm). Retention times: R (minor) 7.50 min, S (major) 10.48 min.40aToluene proved to be the better solvent for the reaction since a slight decrease in ee to 72percent was observed when catalyst 75a was used in cyclohexane. Conditions where an additive, such as titanium(IV) isopropoxide. were also attempted with catalyst 75a. but both a low yield and low ee's were obtained (4percent and 6percent. respectively). Only results from the standard reaction conditions are shown in Table 14.Both diastereomers of the secondary alcohols were examined as catalysts in the reaction, shown in entries 2-9. Interestingly, only diastereomers with the absolute configuration of 74a-d had a significant effect on the enantioselectivity. In addition, in every case where a significant enatioselectivity was observed, the primary product was the R enantiomer.Compound 74d (entry 9) gave the highest enantiomeric excess for this class of ligands: however, the 1-naphthyl substituted ligand 74c provided a similar ee of 76percent with an 83percent yield. In the case of 74d. the electron-withdrawing effect of the fluorines on the aromatic ring created a decrease in the yield as compared to 74a-c.When comparing the selectivity provided by catalysts 74c and 74d (76percent ee and 79percent ee. respectively) with 74a and 74b (both 64percent ee) it appears that selectivity can be increased by either

83/258

2018-07-03 17:29:03

adding more electron withdrawing substituents or increasing the steric hindrance. These findings were also observed in the series of tertiary alcohols 75a-d. The decafluorobenzophenone tertiary alcohol 75d gave a 95percent ee, while the benzophenone tertiary alcohol 75a only gave 79percent ee (entries 10 and 13). The greater steric bulk of 75b gave an ee of 83percent. while the smaller tertiary alcohol 75c only afforded 66percent ee (entries 11 and 12). Table 3: Secondary and tertiary alcohols as ligands in the catalytic asymmetric addition of diethylzinc to benzaldehydeEt2Zn (2.2 equiv), catalyst (0.2 equiv) toluene. 0 0C, 24 h 15 17"Determined by chiral HPLC on column C hiralcel OD with /. = 219 iim. 10° o ;-pi opanol liexanes a> the eluent with a flow rate of 1.00 niL mm. Lower yield due to difficulties m purificationIn general, the tertiary alcohols, entries 10, 11, and 13. enhanced the selectivity of the reaction more than the secondary alcohols. The decafluoro tertiary alcohol 75d proved to provide one of the best enantioselectivities (95percent ee) overall, but gave the lowest yield.Surprisingly, the increased steric bulk provided by the tert-butyl groups on compound 75c did not improve the selectivity over that afforded by 75d and even decreased the selectivity when compared to the smaller compound 75a. Gau and Wu discovered with their η-amino alcohol systems that aromatic substituents increased the ee, while alkyl substituents decreased the ee (Gau, H. M.; Wu, K. H. Or ganomet allies 2003, 22, 5193-5200). Their finding is consistent with the results in Table 14 when comparing the tertiary and secondary alcohols. For example, the additional phenyl group on 75a (Table 3, entry 10) causes an increase in the selectivity by about 10 percent ee over that of entry 3. This shows that increase in steric bulk of the catalyst does help to increase enantioselectivity. However, catalyst 75b did not seem to show much of an increase in yield or selectivity from 75a suggesting that the 2-naphthyl substituents do not increase the sterics much from the phenyl substituents.Upon determining 75d as the catalyst with the highest selectivity at 20 mol percent, the asymmetric reaction parameters were optimized by varying the conditions of the reaction by lowering the catalyst loading (Table 4). When going from 20 mol percent to 10 mol percent of catalyst 75d, only a slight change in percent yield and percent ee were observed. Much to our delight, the reaction went further to completion when 5 mol percent of catalyst 75d was employed in the reaction than when 10 percent was used. However, when the amount of catalyst was further reduced to 2 mol percent of 75d, a decrease in the yield and selectivity was observed (Table 4, entry 4).Table 4: Variation of the catalyst loading using 75d as the ligand for the diethylzinc addition to benzaldehydeaLo\\ver yield due to difficulties in purification.Using the optimized asymmetric reaction conditions. 75d was used to catalyze the addition of diethylzinc to other aldehyde substrates as shown in Table 5. The -Cl and - OCHs substituents on the aromatic ring did not seem to have a large effect on the enantiocontrol of the reaction (entries 2 and 3) and afforded results similar to benzaldehyde; however, the yield of the reaction was lower with chlorobenzaldehyde as the substrate. When cinnamaldehyde and hydrocinnamaldehyde were employed in the reaction, a decrease in the enantioselectivity was observed.Table 5: Diethylzinc additions to aldehydes catalyzed by 75d (5 mol percent)Overall, the novel nicotine-based decafluorodiphenyl catalyst demonstrates respectable yields and high enantioselectivities when employed in the catalytic asymmetric addition of diethylzinc to aromatic aldehydes. Finally, to investigate the effect of the chlorine substituent on the nicotine-based catalysts during the asymmetric reaction, compounds 9028 and 91 were synthesized and compared to 75a (Schemes 3 and 4). This comparison would provide insight as to whether or not the C-4 substituted nicotine-based compounds could be improved to enhance selectivity in the asymmetric reaction by adding or removing chlorine substituents from the pyridine ring.Scheme 3: Synthesis of 9090Scheme 4: Synthesis of 91Addition of a chlorine substituent to the C-5 position of nicotine, as shown with compound 90, increased the selectivity to 95percent ee at 20 mol percent, but at 5 mol percent a slight decrease in selectivity was observed (Table 6, entries 3 and 4). In contrast, catalyst 91 with no chlorine substituents decreased the selectivity as compared to ligand 75a as seen in Table 6, entries 5 and 6. The selectivity and yield were worse when the amount of catalyst 91 was lowered to 5 mol percent. Therefore, it may be desirable to have at least one chlorine substituent on the nicotine portion of the molecule, in addition to the alcohol functionality off of the C-4 position, in order to maintain adequate selectivity in the asymmetric reaction. Table 6: Comparing catalysts 75a, 75d, 90 and 91 in the asymmetric reaction of diethylzinc and benzaldehydea aReacrioηs were run at 0 ~C for 24 h in toluene.In conclusion, the more sterically hindered C-4 tertiary alcohols of (ηS)-6-chloronicotine provided better enantio selectivity than the C-4 secondary alcohols. Additionally, electron withdrawing fluorines on the aromatic ring improved the ee as compared to electron donating groups, as seen when comparing catalyst 75d with 75a and 75c. The effect of the chlorines on the pyridine ring of nicotine also proved to be beneficial when applied to the asymmetric reaction. Two chlorine substituents on nicotine derivative 90 proved to be superior to only one chlorine substituent on molecule 75a. When no chlorines were on C-4 substituted 91, the yield and the selectivity decreased noticeably.Overall, compound 75d provided the most promising results, yielding an ee of 95percent when benzaldehyde was the substrate and only 5 mol percent of the catalyst was used. The catalyst also provided acceptable results when other substrates were employed in the asymmetric reaction.However, compound 75d with zinc(II) triflate yielded very little product was obtained (data not shown). The diethylzinc conditions were applied where the product 93 was obtained with a 93percent yield with a 13percent ee, but some ethylphenyl alcohol 17 was also observed. In addition, when applied to the Henry reaction, the yields were very low (data not shown). Stage 1: With [5-((2S)-1-methylpyrrolidin-2-yl)-2-chloro(4-pyridyl)]dinaphthalen-2-ylmethan-1-ol in hexane, toluene, Time= 0.5h, T= 0 °C Stage 2: in hexane, toluene, Time= 24h Stage 3: With water, ammonium chloride in hexane, toluene Patent; NORTH CAROLINA STATE UNIVERSITY; COMINS, Daniel, L.; CAPRACOTTA, Sonja, S.; WO2010/40059; (2010); (A1) English View in Reaxys

84/258

2018-07-03 17:29:03

Stage 1: With titanium(IV) isopropylate, (S)-3-(1H-benzimidazol-1-yl)-1,1'-bi-2-naphthol in dichloromethane, toluene, Time= 0.5h, Inert atmosphere Stage 2: in dichloromethane, toluene, Time= 5h, T= 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Zhang, Zhi-Guang; Dong, Zhi-Bing; Li, Jin-Shan; Chirality; vol. 22; nb. 9; (2010); p. 820 - 826 View in Reaxys Stage 1: With C31H31NO3 in hexane, toluene, Time= 0.5h, T= 20 °C , Inert atmosphere Stage 2: in hexane, toluene, Time= 24h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Xu, Geng; Liu, Zhan Zhu; Chinese Chemical Letters; vol. 21; nb. 3; (2010); p. 309 - 311 View in Reaxys With n-butyllithium, (-)-[(2S,4R)-1-cyclohexyl-4-methylpiperidin-2-yl]methanol in toluene, Time= 18h, T= 20 - 23 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Alvarez-Ibarra, Carlos; Lujan, Juan F. Collados; Quiroga-Feijoo, Maria L.; Tetrahedron Asymmetry; vol. 21; nb. 19; (2010); p. 2334 - 2345 View in Reaxys With titanium(IV) isopropylate in hexane, dichloromethane, Time= 6h, T= 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Liu, Xiao; Wang, Peiyuan; Zhang, Lei; Yang, Jie; Li, Can; Yang, Qihua; Chemistry - A European Journal; vol. 16; nb. 42; (2010); p. 12727 - 12735 View in Reaxys With titanium(IV) isopropylate, 2C2H6O*5.3C3H7NO*C48H26O10 (4-)*5H2O*2Zn(2+) in toluene, optical yield given as percent ee Ma, Liqing; Wu, Chuan-De; Wanderley, Marcela M.; Lin, Wenbin; Angewandte Chemie - International Edition; vol. 49; nb. 44; (2010); p. 8244 - 8248 View in Reaxys Stage 1: With (S)-2-(5-benzyl-4-isopropyl-5,6-dihydro-4H-1,3,4-oxadiazin-2-yl)-6-methylphenol in hexane, toluene, Time= 0.416667h, T= 20 °C , Inert atmosphere Stage 2: in hexane, toluene, Time= 24h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Dean, Melissa A.; Hitchcock, Shawn R.; Tetrahedron Asymmetry; vol. 21; nb. 20; (2010); p. 2471 - 2478 View in Reaxys Stage 1: With (1S,2S,5R)-2-isopropyl-5-methyl-1-[2-{(S)-6-phenylpyridin-2-yl}phenyl]-cyclohexanol in toluene, T= 0 - 20 °C , Inert atmosphere Stage 2: in toluene, Time= 96h, T= 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Leven, Matthias; Schloerer, Nils E.; Neudoerfl, Joerg M.; Goldfuss, Bernd; Chemistry - A European Journal; vol. 16; nb. 45; (2010); p. 13443 - 13449 View in Reaxys Stage 1: With (1S,2S,5S)-4,6,6-trimethyl-2-[2-{(S)-6-phenylpyridin-2-yl}phenyl]bicyclo-[3.1.1]hept-3-en-2-ol in toluene, T= 0 - 20 °C , Inert atmosphere Stage 2: in toluene, Time= 96h, T= 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Leven, Matthias; Schloerer, Nils E.; Neudoerfl, Joerg M.; Goldfuss, Bernd; Chemistry - A European Journal; vol. 16; nb. 45; (2010); p. 13443 - 13449 View in Reaxys Stage 1: With (3R,4R)-3,4-diphenyl-2,5-diazabicyclo[4.2.0]oct-1(6)-ene-7,8-dione in hexane, dichloromethane, Time= 0.5h, T= -78 - -20 °C , Inert atmosphere Stage 2: in hexane, dichloromethane, T= -78 - 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Jin, Xiaoqing; Min, Qiaoqiao; Zheng, Yangfan; Wang, Pengcheng; Zhu, Jun; Zhou, Hai-Bing; Arkivoc; vol. 2010; nb. 11; (2010); p. 322 - 335 View in Reaxys

85/258

2018-07-03 17:29:03

Stage 1: With titanium(IV) isopropylate, (R,R)-1,2-dibenzylsulfonamidecyclohexane in hexane, toluene, Time= 20h, T= 20 °C Stage 2: With water in hexane, toluene, optical yield given as percent ee, enantioselective reaction Cortez, Norma A.; Aguirre, Gerardo; Parra-Hake, Miguel; Somanathan, Ratnasamy; Arita, Amy J.; Cooksy, Andrew L.; De Parrodi, Cecilia Anaya; Huelgas, Gabriela; Synthetic Communications; vol. 41; nb. 1; (2011); p. 73 - 84 View in Reaxys With (R)-2-(6-methoxy-1-(2-methoxyphenyl)-3,4-dihydroisoquinolin-2(1H)-yl)-1,1-diphenylethanol in hexane, T= 0 - 20 °C , Inert atmosphere, optical yield given as percent ee Hari, Yoshiyuki; Sakuma, Masaki; Miyakawa, Ayako; Hatano, Keiichiro; Aoyama, Toyohiko; Heterocycles; vol. 76; nb. 1; (2008); p. 305 - 311 View in Reaxys With (R)-2-(6-methoxy-1-(2-methoxyphenyl)-3,4-dihydroisoquinolin-2(1H)-yl)ethanol in hexane, T= 0 - 20 °C , Inert atmosphere, optical yield given as percent ee Hari, Yoshiyuki; Sakuma, Masaki; Miyakawa, Ayako; Hatano, Keiichiro; Aoyama, Toyohiko; Heterocycles; vol. 76; nb. 1; (2008); p. 305 - 311 View in Reaxys With (2S)-3-ethyl-2-(octahydro-2H-4,7-ethanoisoindol-2-yl)-1-phenylpentan-3-ol in toluene, Time= 24h, T= -30 °C , optical yield given as percent ee, enantioselective reaction Sahin, Engin; Kilic, Hamdullah; Tetrahedron Asymmetry; vol. 22; nb. 3; (2011); p. 277 - 282 View in Reaxys 4.8. Typical procedure for the addition of diethylzinc to aldehyde General procedure: A solution of diethylzinc (1.5 mL of 1 M hexane solution, 1.5 mmol) was added dropwise to a solution of ligand 2 (0.05 mmol, 10 mol percent) in dry THF (2 mL) under an argon atmosphere and the mixture was stirred at room temperature for 1 h. The mixture was cooled to 0 °C and a solution of benzaldehyde (0.5 mmol) in dry THF (1 mL) was added with a syringe. After stirring for 30 h, the reaction was quenched by the addition of saturated aqueous NH4Cl (4 mL) and diphenylmethane (42 mg, 0.25 mmol) was added as an internal standard. The mixture was extracted with EtOAc (3 .x. 8 mL). The combined organic layers were washed with brine, dried over anhydrous Na2SO4, and evaporated under reduced pressure. The conversion and yield were determined by 1H NMR analysis directly on the crude mixture. The crude product was purified by preparative radial thinlayer chromatography (Chromatotron) over silica gel eluting with hexane/EtOAc (90:10) and the enantiomeric excess of the product was determined by GC on a Chiral η-DEX 120 capillary column. Stage 1: With (1S,1'S)-1,1'-(4,4'-biquinazoline-2,2'-diyl)bis(2,2-dimethylpropan-1-amine) in hexane, Time= 1h, T= 20 °C , Inert atmosphere Stage 2: in hexane, Time= 30h, T= 0 - 20 °C , Inert atmosphere Stage 3: With water, ammonium chloride in hexane, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Cakici, Murat; Catir, Mustafa; Karabuga, Semistan; Ulukanli, Sabri; Kilic, Hamdullah; Tetrahedron Asymmetry; vol. 22; nb. 3; (2011); p. 300 - 308 View in Reaxys Stage 1: With titanium(IV) isopropylate in hexane, dichloromethane, Time= 4h, T= 0 °C , Inert atmosphere Stage 2: With ammonium chloride in hexane, dichloromethane, enantioselective reaction Zhang, Lei; Guo, Yanan; Peng, Juan; Liu, Xiao; Yuan, Pei; Yang, Qihua; Li, Can; Chemical Communications; vol. 47; nb. 14; (2011); p. 4087 - 4089 View in Reaxys 4.10. Typical procedure for asymmetric addition of Et2Zn to aldehydes General procedure: Diethylzinc (2 mmol, 2 ml, 1 M solution in hexanes) was added to a solution of chiral Schiff base 4d (79.92 mg, 0.20 mmol) in dry toluene (5 ml) at -70 °C under an atmosphere of N2. After 1 h, the aldehyde (1 mmol) was added and the reaction mixture was warmed to room temperature. The mixture was stirred for the appropriate time (Scheme 3) and was quenched with a saturated solution of ammonium chloride (5 ml). After 10 min of stirring, the mixture was extracted with ethyl acetate (3 .x. 10 ml), dried over anhydrous MgSO4 and gravity filtered. The solvent was evaporated to obtain enantiomerically enriched 1-phenyl-1-propanol. The crude product was purified by column chromatography using appropriate eluents (hexane/ ethyl acetate). The ee was determined with HPLC using Chiralcel OD-H column or GC analysis using η-Dex capillary column. Yields were determined via GC analysis using ZB-5 capillary column or by isolation of the product ([Table 2] and [Table 3]).

86/258

2018-07-03 17:29:03

Stage 1: With 2-tert-butyl-6-((E)-((1S,2S,3R,5S)-3-(hydroxymethyl)-2,6,6-trimethylbicyclo[3.1.1]heptan-2-ylimino)methyl)-4methylphenol in hexane, toluene, Time= 24h, T= -70 - 20 °C , Inert atmosphere Stage 2: With ammonium chloride in hexane, water, toluene, Time= 0.166667h, Saturated solution, optical yield given as percent ee, enantioselective reaction Jaworska, Magdalena; Blocka, Ewelina; Kozakiewicz, Anna; Welniak, Miroslaw; Tetrahedron Asymmetry; vol. 22; nb. 6; (2011); p. 648 - 657 View in Reaxys 4.10. Typical procedure for asymmetric addition of Et2Zn to aldehydes General procedure: Diethylzinc (2 mmol, 2 ml, 1 M solution in hexanes) was added to a solution of chiral Schiff base 4d (79.92 mg, 0.20 mmol) in dry toluene (5 ml) at -70 °C under an atmosphere of N2. After 1 h, the aldehyde (1 mmol) was added and the reaction mixture was warmed to room temperature. The mixture was stirred for the appropriate time (Scheme 3) and was quenched with a saturated solution of ammonium chloride (5 ml). After 10 min of stirring, the mixture was extracted with ethyl acetate (3 .x. 10 ml), dried over anhydrous MgSO4 and gravity filtered. The solvent was evaporated to obtain enantiomerically enriched 1-phenyl-1-propanol. The crude product was purified by column chromatography using appropriate eluents (hexane/ ethyl acetate). The ee was determined with HPLC using Chiralcel OD-H column or GC analysis using η-Dex capillary column. Yields were determined via GC analysis using ZB-5 capillary column or by isolation of the product ([Table 2] and [Table 3]). Stage 1: With 2,4-di-tert-butyl-6-((E)-((1S,2S,3R,5S)-3-(hydroxymethyl)-2,6,6-trimethylbicyclo[3.1.1]heptan-2-ylimino)methyl)phenol in hexane, toluene, Time= 48h, T= -70 - 20 °C , Inert atmosphere Stage 2: With ammonium chloride in hexane, water, toluene, Time= 0.166667h, Saturated solution, optical yield given as percent ee, enantioselective reaction Jaworska, Magdalena; Blocka, Ewelina; Kozakiewicz, Anna; Welniak, Miroslaw; Tetrahedron Asymmetry; vol. 22; nb. 6; (2011); p. 648 - 657 View in Reaxys With titanium(IV) isopropylate, (R)-1,1'-Bi-2-naphthol in dichloromethane, Time= 4h, T= 0 °C , optical yield given as percent ee, enantioselective reaction Liu, Xiao; Wang, Peiyuan; Yang, Yan; Wang, Peng; Yang, Qihua; Chemistry - An Asian Journal; vol. 5; nb. 5; (2010); p. 1232 - 1239 View in Reaxys Stage 1: With (1R,2S,3S,4S)-(+)-2-benzyloxy-3-(6-methylpyrid-2-yl)-1,7,7-trimethylbicyclo[2.2.1]heptan-3-ol in hexane, toluene, Time= 0.5h, T= 20 °C , Inert atmosphere Stage 2: in hexane, toluene, Time= 48h, T= 20 °C , Inert atmosphere Stage 3: With hydrogenchloride, water in hexane, toluene, optical yield given as percent ee Boyle, Grant A.; Govender, Thavendran; Kruger, Hendrik G.; Maguire, Glenn E.M.; South African Journal of Chemistry; vol. 62; (2009); p. 113 - 123 View in Reaxys Stage 1: With N-(2-hydroxybenzylidene)-(S)-phenylethylamine in hexane, toluene, Inert atmosphere, Cooling Stage 2: in hexane, toluene, T= 20 °C , Cooling, Inert atmosphere, optical yield given as percent ee Jaworska, Magdalena; Welniak, Miroslaw; Zieciak, Justyna; Kozakiewicz, Anna; Wojtczakb, Andrzej; Arkivoc; vol. 2011; nb. 9; (2011); p. 189 - 204 View in Reaxys 4.6. General experimental procedure for the reactions of aldehydes with diethylzinc in the presence of chiral catalyst 5-14 or 17-21 General procedure: To the respective catalyst (0.1 mmol) 5-14 or 17-21, 1 M Et2Zn in n-hexane solution (3 mL, 3 mmol) was added under an Ar atmosphere at room temperature. The reaction was stirred for 25 min at room temperature, and the aldehyde (1 mmol) was then added to the solution, with subsequent stirring at room temperature for a further 20 h. The reaction was quenched with a saturated NH4Cl solution (15 mL) and the mixture was extracted with EtOAc (2 .x. 20 mL). The combined organic phase was washed with water (10 mL), dried (Na2SO4) and evaporated under vacuum. The crude secondary alcohols obtained were purified by flash column chromatography (n-hexane/EtOAc = 4:1). Stage 1: With (1aR,2aR,6aR,7aS)-6a-hydroxy-1,1-dimethyl-5-((S)-1-phenylethyl)decahydro-3-oxa-5-azacyclopropa[g]naphthalene in hexane, Time= 20h, T= 20 °C , Inert atmosphere Stage 2: With ammonium chloride in hexane, Saturated solution, optical yield given as percent ee, enantioselective reaction

87/258

2018-07-03 17:29:03

Szakonyi, Zsolt; Csillag, Kinga; Fueloep, Ferenc; Tetrahedron Asymmetry; vol. 22; nb. 9; (2011); p. 1021 - 1027 View in Reaxys 4.6. General experimental procedure for the reactions of aldehydes with diethylzinc in the presence of chiral catalyst 5-14 or 17-21 General procedure: To the respective catalyst (0.1 mmol) 5-14 or 17-21, 1 M Et2Zn in n-hexane solution (3 mL, 3 mmol) was added under an Ar atmosphere at room temperature. The reaction was stirred for 25 min at room temperature, and the aldehyde (1 mmol) was then added to the solution, with subsequent stirring at room temperature for a further 20 h. The reaction was quenched with a saturated NH4Cl solution (15 mL) and the mixture was extracted with EtOAc (2 .x. 20 mL). The combined organic phase was washed with water (10 mL), dried (Na2SO4) and evaporated under vacuum. The crude secondary alcohols obtained were purified by flash column chromatography (n-hexane/EtOAc = 4:1). Stage 1: With (1S,3R,4R,6R)-7,7-dimethyl-3-(((S)-1-phenylethylamino)methyl)bicyclo[4.1.0]heptane-3,4-diol in hexane, Time= 20h, T= 20 °C , Inert atmosphere Stage 2: With ammonium chloride in hexane, Saturated solution, optical yield given as percent ee, enantioselective reaction Szakonyi, Zsolt; Csillag, Kinga; Fueloep, Ferenc; Tetrahedron Asymmetry; vol. 22; nb. 9; (2011); p. 1021 - 1027 View in Reaxys 4.6.1. General procedure D General procedure: A mixture of 2s (0.0060 mmol) and diethylzinc (0.40 mL, 0.40 mmol; 1.05 M solution in hexane) in hexane (1.00 mL) was stirred at room temperature for 1 h. Then the mixture was cooled to appropriate temperature, added aldehyde 3 (0.200 mmol), and stirred for 24 h. The mixture was then quenched by NH4Cl aq and extracted with EtOAc three times. The combined organic layers were washed with brine and dried over Na2SO4. The crude product was purified by PTLC on silica gel (EtOAc/hexane = 1:4) to give 4. Stage 1: With N-[(1S)-1-(2,3-dimethoxyphenyl)ethyl]-4-methylbenzenesulfonamide in hexane, Time= 1h, T= 20 °C , Inert atmosphere Stage 2: in hexane, Time= 24h, T= 20 °C , Inert atmosphere Stage 3: With ammonium chloride in hexane, water, optical yield given as percent ee, enantioselective reaction Yoshida, Kazuhiro; Akashi, Naohisa; Yanagisawa, Akira; Tetrahedron Asymmetry; vol. 22; nb. 11; (2011); p. 1225 - 1230 View in Reaxys Stage 1: With titanium(IV) isopropylate, 3-O-acetyl-1,2-O-isopropylidene-η-L-idofuranose in hexane, dichloromethane, Time= 6h, T= 20 °C , Inert atmosphere Stage 2: With water, ammonium chloride in hexane, dichloromethane, Inert atmosphere, optical yield given as percent ee, enantioselective reaction Parada, Jose; Mendoza, Jorge; Cisternas, Francy; Eguiluz, Angel; Journal of the Chilean Chemical Society; vol. 55; nb. 4; (2010); p. 428 - 430 View in Reaxys With C20H23N3O3S in toluene, Time= 24h, T= 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Karabuga, Semistan; Cakici, Murat; Kazaz, Cavit; Sahin, Ertan; Kilic, Hamdullah; Ulukanli, Sabri; Organic and Biomolecular Chemistry; vol. 9; nb. 22; (2011); p. 7887 - 7896 View in Reaxys Stage 1: With (1S,2R)-7,7-dimethyl-1-[(morpholin-4-yl)carbonyl]norbornan-2-ol in hexane, Time= 0.5h, T= 20 °C , Inert atmosphere Stage 2: in hexane, Time= 5h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Sanchez-Carnerero, Esther M.; De Las Casas Engel, Tomas; Maroto, Beatriz Lora; De La Moya Cerero, Santiago; Arkivoc; vol. 2011; nb. 10; (2011); p. 351 - 359 View in Reaxys With 1,3-bis((S)-1-hydroxy-1,1,3-triphenylpropan-2-yl)thiourea in hexane, toluene, T= 20 °C , optical yield given as percent ee, enantioselective reaction Qiao, Zhi Guo; Shen, Tian Hua; Fu, Zhen Fang; Li, Jun Qi; Wang, Hong; Song, Qing Bao; Chinese Chemical Letters; vol. 22; nb. 11; (2011); p. 1265 - 1268 View in Reaxys

88/258

2018-07-03 17:29:03

Stage 1: With C24H38N2O4 in hexane, Time= 5h, T= 20 °C , Inert atmosphere Stage 2: With hydrogenchloride, water, optical yield given as percent ee, enantioselective reaction Sanchez-Carnerero, Esther M. Marquez; De Las Casas Engel, Tomas; Lora Maroto, Beatriz; De La Moya Cerero, Santiago; Chirality; vol. 23; nb. 7; (2011); p. 523 - 526 View in Reaxys With titanium(IV) isopropylate, (1S,2R,4S,5R)-2,5-dimethyl-1,4-N,N'-biscamphorsulfonamino-2,5-dimethylcyclohexane in hexane, toluene, Time= 10h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Yang, Minghua; Sun, Jiangtao; Zhu, Chengjian; Chinese Journal of Chemistry; vol. 29; nb. 8; (2011); p. 1697 - 1702 View in Reaxys Stage 1: With (1R,2S,4R,5S)-1,4-N,N-bis(p-methylphenylsulfonamino)-2,5-dimethylcyclohexane in hexane, toluene, Time= 0.333333h, T= 20 °C , Inert atmosphere Stage 2: With titanium(IV) isopropylate in hexane, toluene, Time= 0.5h, T= -78 °C , Inert atmosphere Stage 3: in hexane, toluene, Time= 18h, T= -25 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Yang, Minghua; Sun, Jiangtao; Zhu, Chengjian; Chinese Journal of Chemistry; vol. 29; nb. 8; (2011); p. 1697 - 1702 View in Reaxys 4.3.1. (R)-1-Phenylpropan-1-ol 14a A flame-dried Schlenk flask was charged with 7 (27 mg, 0.12 mmol) evacuated and purged with argon. Toluene (1.0 mL) was added followed by diethylzinc (1 M in hexanes, 2.00 mL, 2.00 mmol), the resulting mixture was stirred at rt for 20 min and benzaldehyde (0.10 mL, 1.0 mmol) was added at 0 °C. The mixture was allowed to warm to rt and stirring was continued for 16 h. The reaction was quenched by the addition of aq 1 M HCl (10 mL) followed by EtOAc (20 mL). The phases were separated and the aqueous layer was extracted with EtOAc (3 .x. 20 mL). The combined organic layers were washed with brine, dried with Na2SO4, filtered, and the solvent was removed under reduced pressure. The crude product was purified by flash column chromatography on silica gel (hexane/EtOAc = 4:1) to afford 112 mg (82percent) of 14a as colorless oil. [η]D = +37.8 (c 1.0, CHCl3); lit.: [η]D = +45.4 (c 0.5, CHCl3) for 98percent ee.refPreviewPlaceHolder19 1H NMR (250 MHz, CDCl3): η = 0.89 (t, J = 7.4 Hz, 3H, CH2CH3), 1.63-1.89 (m, 2H, CH2CH3), 2.24 (br s, 1H, OH), 4.54 (t, J = 6.6 Hz, 1H, CHOH), 7.25-7.39 (m, 5H, Ph) ppm. 70percent ee determined by HPLC analysis: Daicel Chiralpak IA column, 254 nm UV detector, 2percent i-PrOH in hexane, flow rate: 0.5 mL/min, retention time (R)-enantiomer: 39 min, (S)-enantiomer: 42 min. Stage 1: With (R)-(4-methoxy-6-methylpyridin-2-yl)(phenyl)methanol in hexane, toluene, Time= 0.333333h, T= 20 °C , Inert atmosphere Stage 2: in hexane, toluene, Time= 16h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Eidamshaus, Christian; Reissig, Hans-Ulrich; Tetrahedron Asymmetry; vol. 22; nb. 16-17; (2011); p. 1644 - 1652 View in Reaxys With C11H17NO2 in hexane, toluene, T= 0 - 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Eidamshaus, Christian; Reissig, Hans-Ulrich; Tetrahedron Asymmetry; vol. 22; nb. 16-17; (2011); p. 1644 - 1652 View in Reaxys Stage 1: With 3-phenyl-N-((R)-1-phenylethyl)-2-(tosylamino)propanamide in hexane, toluene, T= 0 - 20 °C , Inert atmosphere Stage 2: in hexane, toluene, Time= 40h, T= 0 °C , Inert atmosphere Stage 3: With hydrogenchloride, water in hexane, toluene, T= 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Gou, Shaohua; Ye, Zhongbin; Chang, Jing; Gou, Guangjun; Feng, Mingming; Applied Organometallic Chemistry; vol. 25; nb. 6; (2011); p. 448 - 453 View in Reaxys 2 :Reaction Example 1Asymmetric Diethylzinc Addition with Benzaldehyde Catalyzed by η-Amino Alcohols B and 5-7The application of 10 mol percent of η-amino alcohols B and 5-7 in the asymmetric addition of diethylzinc with benzaldehydes was initially tested at 0° C., and good yields along with excellent ee were obtained (Table 1). With (1S,2R)-7,7-dimethyl-1-pyrrolidin-1-yl-bicyclo[2.2.1]-heptan-2-ol in hexane, Time= 2h, T= 0 °C Patent; UANG, Biing-Jiun; Wu, Chi-Rui; Wu, Hsyueh-Liang; US2011/313159; (2011); (A1) English View in Reaxys

89/258

2018-07-03 17:29:03

1.i :(i) Asymmetric Addition with Different Amounts of Chiral Ligand; With reference to the following Scheme 4, it shows that ethyl in diethyl zinc is added to the aldehyde in the presence of η-amino thiol 40 used as a chiral ligand. Compound 40 (the used amount thereof listed in Table 1) and benzaldehydes (2 mmol) placed in a 10-ml round-bottomed flask were stirred for 10 minutes at predetermined temperatures (shown in Table 1).Subsequently, diethyl zinc in n-hexane (1 M, 3 ml, 3 mmol) was added slowly along the inner wall of the flask. Posterior to several hours (shown in Table 1) of stirring, NH4Cl aqueous solution (1 N, 1 ml) was added to cease reaction, and then 1 N HCl aqueous solution was added for neutralization (pH=7). The organic and water phases were separated and the water phase was extracted with dichloromethane (20 ml.x.3). The organic phase collected was dried with anhydrous sodium sulfate, filtrated, and then condensed. The crude extract was purified by chromatography (eluent:ethyl acetate:n-hexane=1:6) to give the adduct and the results are listed in Table 1. Stage 1: With (2R)-2-aminomethyl-2-benzyl-sulfanyl-7,7-dimethyl-bicyclo[2.2.1]hept-1-yl-N,N-diisopropyl-methanesulfonamide, Time= 0.166667h, T= 20 °C Stage 2: in hexane, Time= 10h, T= 20 °C Stage 3: With ammonium chloride in hexane, water, Product distribution / selectivity Patent; UANG, Biing-Jiun; Yang, Bo-Yao; US2012/77976; (2012); (A1) English View in Reaxys Stage 1: With (R)-2-ethylthio-4-hydroxymethyl-4,5-dihydro-1,3-thiazole in hexane, toluene, Time= 0.5h, T= 0 °C Stage 2: in hexane, toluene, Time= 48h, T= 0 - 20 °C , optical yield given as percent ee, enantioselective reaction Gong, Zhiyong; Liu, Qingwen; Xue, Pengchong; Li, Kechang; Song, Zhiguang; Liu, Zaiqun; Jin, Yinghua; Applied Organometallic Chemistry; vol. 26; nb. 3; (2012); p. 121 - 129 View in Reaxys Stage 1: With (1R,2S,3R,6R)-3,7,7-trimethyl-3-(methylamino)bicyclo[4.1.0]heptane-2-methanol in hexane, Time= 0.333333h, T= 20 °C Stage 2: in hexane, Time= 20h, T= 0 °C , optical yield given as percent ee Koneva; Korchagina; Genaev; Volcho; Salakhutdinov; Russian Journal of Organic Chemistry; vol. 48; nb. 1; (2012); p. 32 39 View in Reaxys Stage 1: With 2-{(1S,2S,3R,6R)-3-hydroxymethyl-3,7,7-trimethylbicyclo[4.1.0]heptan-2-ylaminomethyl}phenol in hexane, Time= 0.333333h, T= 20 °C Stage 2: in hexane, Time= 20h, T= 0 °C , optical yield given as percent ee Koneva; Korchagina; Genaev; Volcho; Salakhutdinov; Russian Journal of Organic Chemistry; vol. 48; nb. 1; (2012); p. 32 39 View in Reaxys Stage 1: With diphenyl[(2S)-1-[(2,4,6-trimethylphenyl)methyl]pyrrolidin-2-yl]methanol in hexane, dichloromethane, Time= 2h, T= 20 °C , Inert atmosphere Stage 2: in hexane, dichloromethane, Time= 24h, T= 20 °C , Inert atmosphere Stage 3: With hydrogenchloride in hexane, dichloromethane, water, Inert atmosphere, enantioselective reaction Xu, Zhou; Bo, Rongcheng; Wu, Nan; Wan, Yu; Wu, Hui; Letters in Organic Chemistry; vol. 8; nb. 8; (2011); p. 582 - 586 View in Reaxys Stage 1: With (1S,2R,4R)-1-{[4-(2-hydroxyethyl)piperazin-1-yl]carbonyl}-7,7-dimethylnorbornan-2-ol in hexane, Time= 0.0833333h, T= 20 °C , Inert atmosphere Stage 2: in hexane, Time= 5h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Sanchez-Carnerero, Esther M. Marquez; Engel, Tomas De Las Casas; Maroto, Beatriz Lora; Cerero, Santiago De La Moya; Chirality; vol. 24; nb. 3; (2012); p. 255 - 261 View in Reaxys Stage 1: With (1S,2R,4R)-1-{[4-(2-hydroxyphenyl)piperazin-1-yl]carbonyl}-7,7-dimethylnorbornan-2-ol in hexane, Time= 0.0833333h, T= 20 °C , Inert atmosphere Stage 2: in hexane, Time= 5h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Sanchez-Carnerero, Esther M. Marquez; Engel, Tomas De Las Casas; Maroto, Beatriz Lora; Cerero, Santiago De La Moya; Chirality; vol. 24; nb. 3; (2012); p. 255 - 261 View in Reaxys

90/258

2018-07-03 17:29:03

4.12. General procedure for the reaction of aldehydes with diethylzinc in the presence of chiral catalyst (-)-5-(-)-15 General procedure: To the respective catalyst (0.1 mmol) 5-15, 1 M Et2Zn in n-hexane solution (3 mL, 3 mmol) was added under an argon atmosphere at room temperature. The reaction was stirred for 25 min at room temperature, and benzaldehyde (1 mmol) was then added to the solution, with subsequent stirring at room temperature for a further 20 h. The reaction was quenched with a saturated NH4Cl solution (15 mL) and the mixture was extracted with EtOAc (2 .x. 20 mL). The combined organic phase was washed with H2O (10 mL), dried (Na2SO4) and evaporated under vacuum. The crude secondary alcohols obtained were purified by flash column chromatography (n-hexane/EtOAc = 4:1). The enantiomeric excess and absolute configuration of the resulting material were determined by chiral GC, using a chiral stationary phase (Chirasil-Dex CB column) at 90 °C for 1-phenyl-1-propanol 17 and 18 [tR1 = 7.0 min for the (S)-isomer, tR2 = 8.1 min for the (R)-isomer]. [33] and [34] The direction of the specific rotation of each product was also checked. Stage 1: With (1R,2R,3S,5R)-3-benzylamino-2-hydroxymethyl-6,6-dimethylbicyclo[3.1.1]heptan-2-ol in hexane, Time= 0.416667h, T= 20 °C , Inert atmosphere Stage 2: in hexane, Time= 20h, T= 20 °C , Inert atmosphere Stage 3: With water, ammonium chloride in hexane, optical yield given as percent ee, enantioselective reaction Csillag, Kinga; Nemeth, Lukacs; Martinek, Tamas A.; Szakonyi, Zsolt; Fueloep, Ferenc; Tetrahedron Asymmetry; vol. 23; nb. 2; (2012); p. 144 - 150 View in Reaxys Stage 1: With (S)-1,1-bis(4-methylphenyl)-2-(pyrrolidin-2-yl)ethanol in hexane, toluene, Time= 1h, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, Time= 90h, T= -10 °C , optical yield given as percent ee, enantioselective reaction Liu, Chang-Lu; Wei, Chang-Yong; Wang, Shi-Wen; Peng, Yun-Gui; Chirality; vol. 23; nb. 10; (2011); p. 921 - 928 View in Reaxys With (2S)-N-[(R)-1-hydroxy-3-methylbutan-2-yl]-3-phenyl-2-(tosylamino)propanamide in hexane, toluene, Time= 24h, T= 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Gou, Shaohua; Ye, Zhongbin; Gou, Guangjun; Feng, Mingming; Chang, Jing; Applied Organometallic Chemistry; vol. 25; nb. 2; (2011); p. 110 - 116 View in Reaxys With (2R)-N-[(1R,2S)-1-hydroxy-1-phenylpropan-2-yl]-3-phenyl-2-(tosylamino)propanamide in hexane, toluene, Time= 24h, T= 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Gou, Shaohua; Ye, Zhongbin; Gou, Guangjun; Feng, Mingming; Chang, Jing; Applied Organometallic Chemistry; vol. 25; nb. 2; (2011); p. 110 - 116 View in Reaxys Stage 1: in toluene, Time= 0.5h, T= 20 °C , Inert atmosphere Stage 2: in toluene, Time= 6h, T= 20 °C , Inert atmosphere Stage 3: With ammonium chloride in water, toluene, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Osorio-Planes, Laura; Rodriguez-Escrich, Carles; Pericas, Miquel A.; Organic Letters; vol. 14; nb. 7; (2012); p. 1816 - 1819 View in Reaxys With 2-piperidino-3,3-dimethyl-1-butanol in hexane, Time= 24h, T= -40 - 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Zacharia, Jamest.; Tanaka, Takanori; Uesaka, Yumiko; Hayashi, Masahiko; Synthesis (Germany); vol. 44; nb. 11; (2012); p. 1625 - 1627; Art.No: SS-2012-F0262-OP View in Reaxys With titanium(IV) isopropylate, (S)-N,N'-bis<1-(hydroxymethyl)-2-phenylethyl>ethanediamide in hexane, dichloromethane, Time= 24h, T= 0 °C , Inert atmosphere, optical yield given as percent ee Cetin, Adnan; Asian Journal of Chemistry; vol. 22; nb. 7; (2010); p. 5086 - 5092 View in Reaxys With N,N'-bis[(1S)-2-hydroxyethyl-1-(S)-sec-buthyl]ethanediamide in hexane, dichloromethane, Time= 24h, T= 0 °C , Inert atmosphere, optical yield given as percent ee Cetin, Adnan; Asian Journal of Chemistry; vol. 22; nb. 7; (2010); p. 5086 - 5092

91/258

2018-07-03 17:29:03

View in Reaxys With (1S,8R,9S)-2-(8,10,10-trimethyl-6-aza-tricyclo-[7.1.1.0(2,7)]undeca-2(7),3,5-trien-5-yl)-phenol in hexane, toluene, Time= 30h, T= -40 °C , optical yield given as percent ee, enantioselective reaction Wu, Pei-Shan; Chen, Chinpiao; Journal of the Chinese Chemical Society; vol. 59; nb. 6; (2012); p. 768 - 781 View in Reaxys 4.3. Typical procedure 2 for the catalytic alkylation of benzaldehyde with titanium complexes of amino alcohols General procedure: In a glove box, hexane (1 mL) and a 1 M solution of diethyl zinc in hexane (3.7 mL, 3.7 mmol) were added to a 2 neck 25 mL round bottomed flask. The reaction vessel was taken out of the glove box, and a solution of the ligand (0.0564 mmol, 2 mol percent) dissolved in hexane was added. After stirring for 5 min, the reaction was cooled to -30 °C in a dry ice/ acetone bath. In the glove box, a solution of titanium tetrakis-isopropoxide (16 mg, 0.0564 mmol, 2 mol percent) in hexane (ca. 5 mL) was prepared. The titanium tetrakis-isopropoxide solution was added via syringe, and the reaction was stirred for 10 min. Next, benzaldehyde (0.29 mL, 2.82 mmol) was added via syringe, and the solution allowed to return to room temperature overnight. Work-up and analysis were as described in typical procedure 1. Stage 1: With titanium(IV) isopropylate, N-(2-adamantyl)-1,1-diphenyl-L-valinol in hexane, T= -30 - 20 °C , Inert atmosphere Stage 2: With hydrogenchloride in hexane, water, optical yield given as percent ee, enantioselective reaction Jones, Casey M.; Li, Hanhan; Hickman, Amanda J.; Hughs, Lauren D.; Sobelman, Samuel J.; Johnson, Adam R.; Tetrahedron Asymmetry; vol. 23; nb. 6-7; (2012); p. 501 - 507 View in Reaxys 4.2. Typical procedure 1 for the catalytic alkylation of benzaldehyde with amino alcohols General procedure: In a glove box, hexane (1 mL) and a 1 M solution of diethyl zinc in hexane (3.7 mL, 3.7 mmol) were added to a 2 neck 25 mL round bottomed flask. The reaction vessel was then taken out of the glove box, placed on a nitrogen manifold, and a solution of the ligand (0.0564 mmol, 2 mol percent) dissolved in hexane was added. After stirring for 5 min, the reaction was cooled to -30 °C in a dry ice/acetone bath. Benzaldehyde (0.29 mL, 2.82 mmol) was added via syringe, and the solution allowed to return to room temperature overnight. The reaction was slowly quenched by the addition of hydrochloric acid (2 M, 10 mL). The solution was then separated, extracted with ethyl acetate, washed with a saturated sodium chloride solution, and dried (MgSO4). The solution was then rotary evaporated to give a cloudy liquid, which was chromatographed on silica gel eluting with petroleum ether and ethyl acetate (95:5, 100 mL). Rotary evaporation yielded light-yellow oil, which was used to determine the isolated yield and analyzed by 1H NMR spectroscopy. The product was diluted in ethanol (5 mg/mL) and injected into a chiral GC column (Chiraldex η-DA, 30 m .x. 0.25 μm, 80 °C). Benzaldehyde had a retention time of 7 min; benzyl alcohol had a retention time of 36 min; the two enantiomers of 1-phenylpropanol had retention times of 62 and 63 min for the (S)- and (R)enantiomers, respectively. Stage 1: With N-cyclohexyl-1,1-dimethyl-L-valinol in hexane, T= -30 - 20 °C , Inert atmosphere Stage 2: With hydrogenchloride in hexane, water, optical yield given as percent ee Jones, Casey M.; Li, Hanhan; Hickman, Amanda J.; Hughs, Lauren D.; Sobelman, Samuel J.; Johnson, Adam R.; Tetrahedron Asymmetry; vol. 23; nb. 6-7; (2012); p. 501 - 507 View in Reaxys Stage 1: With N-isopropyl-(S)-2-aminomethyl-1-[2-diphenylhydroxymethyl-6-(trifluoromethyl)phenyl]-1H-pyrrole in hexane, toluene, Time= 1h, T= 20 °C Stage 2: in hexane, toluene, T= 20 °C , optical yield given as percent ee, enantioselective reaction Faigl, Ferenc; Matravolgyi, Bela; Szoellosy, Aron; Czugler, Matyas; Tarkanyi, Gabor; Vekey, Karoly; Kubinyi, Miklos; Chirality; vol. 24; nb. 7; (2012); p. 532 - 542 View in Reaxys Stage 1: With titanium(IV) isopropylate, 3,3'-bis(4-phenyl-1H-1,2,3-triazol-1-yl)-BINOL in toluene, Time= 0.5h, T= 20 - 25 °C , Inert atmosphere Stage 2: in toluene, Time= 15h, T= 20 - 25 °C , Inert atmosphere, optical yield given as percent ee Beckendorf, Stephan; Mancheno, Olga Garcia; Synthesis (Germany); vol. 44; nb. 14; (2012); p. 2162 - 2172; Art.No: SS-2012-C0311-ST View in Reaxys Stage 1: With titanium(IV) isopropylate, (S)-3,3'-bis(4-phenyl-1H-1,2,3-triazol-1-yl)-[1,1'-binaphthalene]-2,2'-diol in toluene, Time= 0.5h, T= 20 - 25 °C , Inert atmosphere Stage 2: in toluene, Time= 15h, T= 20 - 25 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction

92/258

2018-07-03 17:29:03

Beckendorf, Stephan; Mancheno, Olga Garcia; Synthesis (Germany); vol. 44; nb. 14; (2012); p. 2162 - 2172; Art.No: SS-2012-C0311-ST View in Reaxys Stage 1: With titanium(IV) isopropylate, (Sa)-1-[(1S,2R,4R)-2-hydroxy-7,7-dimethylbicyclo[2.2.1]heptan-1-yl]-N-[1-(2-hydroxynaphthalen-1-yl)naphthalen-2-yl]methanesulfonamide in toluene, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in toluene, Time= 1h, T= 0 °C , Inert atmosphere, Solvent, Time, Reagent/catalyst, Overall yield = 95 percent; enantioselective reaction Bian, Guangling; Huang, Huayin; Zong, Hua; Song, Ling; Chirality; vol. 24; nb. 10; (2012); p. 825 - 832 View in Reaxys Stage 1: With titanium(IV) isopropylate, (Sa)-1-[(1S,4R)-7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl]-N-[1-(2-hydroxynaphthalen-1-yl )naphthalen-2-yl]methanesulfonamide in toluene, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in toluene, Time= 2h, T= 0 °C , Inert atmosphere, Solvent, Time, Reagent/catalyst, Overall yield = 94 percent; enantioselective reaction Bian, Guangling; Huang, Huayin; Zong, Hua; Song, Ling; Chirality; vol. 24; nb. 10; (2012); p. 825 - 832 View in Reaxys With (S)-2-anilinomethyl-1-benzylpyrrolidine in hexane, cyclohexane, Time= 18h, T= 20 °C , Inert atmosphere, Reagent/catalyst, Solvent, Overall yield = 87 percent Hosoda, Naoya; Ito, Hiroki; Takimoto, Tatsuya; Asami, Masatoshi; Bulletin of the Chemical Society of Japan; vol. 85; nb. 9; (2012); p. 1014 - 1022 View in Reaxys Stage 1: With N,N'-bis((R,R)-2-diethylaminocyclohexyl)oxalylamide in toluene, Time= 0.5h, T= 20 °C , Inert atmosphere Stage 2: in toluene, Time= 72h, T= -15 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 55 percent; enantioselective reaction Maleev; Gugkaeva; Tsaloev; Moskalenko; Khrustalev; Russian Chemical Bulletin; vol. 61; nb. 1; (2012); p. 51 - 58; Izv. Akad. Nauk, Ser. Khim.; nb. 1; (2012); p. 50 - 57 View in Reaxys With (1R,2R)-1-N-(butan-2-yl)-2-N-(diphenylphosphoryl)-cyclohexane-1,2-diamine in toluene, Time= 0.5h, Reagent/catalyst, Overall yield = 99 percent Huang, Huayin; Zong, Hua; Bian, Guangling; Song, Ling; Journal of Organic Chemistry; vol. 77; nb. 22; (2012); p. 10427 10434 View in Reaxys With (3R,4R)-3-(3-(dimethylamino)propyl)-4,7,7-trimethyl-1',3'-dihydrospiro[bicyclo[2.2.1]-heptane-2,2'-inden]-3-ol, Overall yield = 99 percent Dobrikov, Georgi M.; Philipova, Irena; Nikolova, Rositsa; Shivachev, Boris; Chimov, Angel; Dimitrov, Vladimir; Polyhedron; vol. 45; nb. 1; (2012); p. 126 - 143 View in Reaxys With (1R,2R)-2-(2-(dibenzylamino)ethyl)-1,3,3-trimethylbicyclo[2.2.1]heptan-2-ol, Overall yield = 96 percent Dobrikov, Georgi M.; Philipova, Irena; Nikolova, Rositsa; Shivachev, Boris; Chimov, Angel; Dimitrov, Vladimir; Polyhedron; vol. 45; nb. 1; (2012); p. 126 - 143 View in Reaxys With 2-exo-morpholinoisobornane-10-thiol in hexane, Time= 48h, T= 0 °C , Inert atmosphere, Reagent/catalyst, Time, Temperature, Overall yield = 56 percent; Optical yield = 20 percent ee; enantioselective reaction Cheng, Ying-Ni; Wu, Hsyueh-Liang; Wu, Ping-Yu; Shen, Ying-Ying; Uang, Biing-Jiun; Chemistry - An Asian Journal; vol. 7; nb. 12; (2012); p. 2921 - 2924 View in Reaxys Stage 1: With titanium(IV) isopropylate, C16H14FNO in hexane, Time= 2h, T= 20 °C , Inert atmosphere, Schlenk technique Stage 2: in hexane, Time= 24h, T= 20 °C , Inert atmosphere, Schlenk technique, Reagent/catalyst, Solvent, Temperature, Overall yield = 63 percent; Optical yield = 62 percent ee; enantioselective reaction

93/258

2018-07-03 17:29:03

Wu, Nan; Bo, Rongcheng; Zhang, Rongli; Jiang, Xi; Wan, Yu; Xu, Zhou; Wu, Hui; Letters in Organic Chemistry; vol. 9; nb. 9; (2012); p. 644 - 649 View in Reaxys Stage 1: With 2-(((2S)-2-(hydroxy(diphenyl)methyl)pyrrolidin-1-yl)methyl)-4-nitrophenol in hexane, toluene, Time= 0.5h, T= 25 °C , Inert atmosphere Stage 2: in toluene, Time= 24h, T= 0 °C , Inert atmosphere, Solvent, Temperature, Time, Concentration, Overall yield = 77 percent; enantioselective reaction Gou, Shaohua; Ye, Zhongbin; Feng, Mingming; Jiang, Wenchao; Synthetic Communications; vol. 43; nb. 7; (2013); p. 941 950 View in Reaxys Catalytic reaction with isolated yield. General procedure: Diol 4b (67mg, 0.15 mmol) was mixed with titanium isopropoxide (45μl, 0.15 mmol) in toluene (1.5 ml) solution. The mixture was stirred for 20h at room temperature and then concentrated to dryness. The residue was re-evaporated twice with toluene to remove traces of 2-propanol. The prepared solid was dissolved in toluene (2 ml), titanium isopropoxide (0.4 ml, 1.4 mmol) was added, and the solution was cooled to -40ºC. Then benzaldehyde (102 μl, 1 mmol) was added followed by a dropwise addition of diethylzink (1.4 ml, 1.4 mmol, 1M solution in toluene). The yellowish solution was stirred for 24h at -40ºC and then it was diluted with 10 ml of diethyl ether. GC analyses showed a complete conversion. The precipitate was washed with diethyl ether and the combined filtrates were evaporated (rotavapor 200 mbar) to remove the ether. The obtained toluene solution was purified by flash chromatography first with pentane to remove toluene and then with dichloromethane. The fractions containing the product were collected and the solvent was removed. The prepared liquid (110 mg) contained ~70 wtpercent of the 1-phenylpropanol-1 and the rest was DCM. Yield 57percent (low yield because of the losses during isolation caused by low boiling point of the product). Chiral GC analyses showed 20percent ee of the R-enantiomer. With titanium(IV) isopropylate, 9,9,9',9'-tetramethyldimethylcyclolariciresinol in toluene, Time= 24h, T= -40 °C , Reagent/catalyst, Overall yield = 57 percent; enantioselective reaction Brusentsev, Yury; Sandberg, Thomas; Hotokka, Matti; Sjoeholm, Rainer; Eklund, Patrik; Tetrahedron Letters; vol. 54; nb. 9; (2013); p. 1112 - 1115 View in Reaxys With (S)-2-((S)-1'-phenylethylamino)-1,1,2-triphenylethan-1-ol in hexane, tert-butyl methyl ether, Time= 5h, T= 0 - 20 °C , Inert atmosphere, enantioselective reaction Kang, Seockyong; Baek, Jinho; Ko, Yikyung; Im, Chan; Park, Yongsun; Synlett; vol. 24; nb. 5; (2013); p. 630 - 634; Art.No: ST-2012-U1080-L View in Reaxys General procedure for enantioselective additions of diethylzinc to aldehydes General procedure: To a well-dried Schlenk tube charged with Bu4NBr (32.2 mg, 0.10 mmol, 10 mol percent), a solution of chiral ligand L1 (1 mL, 0.5 mol percent, 0.5 x 10-2 M in toluene) and dry toluene (1.0 mL) was added, then diethylzinc (1.0 M in hexane, 2.0 mL, 2.0 mmol, 2.0 equiv) was slowly added at 0 °C via a syringe under nitrogen atmosphere. After being stirred for 30 min, aldehyde (1a, 106 mg, 101.4 μL, 1.0 mmol) was added dropwise to the mixture at 0 °C . The mixture was stirred for 6 h at room temperature and quenched by addition of aqueous HCl (1.0 M, 5 mL). Extraction with EtOAc (10 mL x 3) gave combined organic layers that were washed with brine (10 mL), dried over MgSO4, and concentrated in vacuo to give a residue that was subjected to silica gel column chromatography (EtOAc/hexane = 1/10), which afforded the corresponding enantio-enriched secondary alcohol (2a) as a colorless oil. The ee value of the secondary alcohol was determined by Chiral GC. The absolute configuration of the alcohol was assigned as (R) by comparison of the optical rotation with reported data. Stage 1: With (1R,2R)-1-N-(diphenylphosphoryl)-2-N-(propan-2-yl)-cyclohexane-1,2-diamine, tetrabutylammomium bromide in hexane, toluene, Time= 0.5h, T= 0 °C , Inert atmosphere, Schlenk technique Stage 2: in hexane, toluene, Time= 6h, T= 0 - 20 °C , Inert atmosphere, Schlenk technique, Reagent/catalyst, Overall yield = 97 percent; enantioselective reaction Zong, Hua; Huang, Huayin; Bian, Guangling; Song, Ling; Tetrahedron Letters; vol. 54; nb. 21; (2013); p. 2722 - 2725 View in Reaxys 4.3 Asymmetric addition of diethylzinc to aldehydes—general procedure General procedure: Chiral catalysts 8a–b or 9a–c (0.1mmol) in dry toluene (5mL) were placed in a round-bottomed flask. The mixture was cooled to 0°C and a solution of diethylzinc (1.0M solution in hexane, 3mmol) was then added under argon. After stirring for 30min, an aldehyde (1mmol) was added at 0°C and the mixture was stirred at room temperature overnight. Next, 5percent aqueous solution of HCl was added, the layers were separated and the aqueous phase was extracted with diethyl ether

94/258

2018-07-03 17:29:03

(4×). The combined organic layers were washed with brine (10mL) and dried over anhydrous MgSO4. The solvents were evaporated to afford the crude alcohols 10a–e, which were purified via column chromatography on silica gel (ethyl acetate with hexane in gradient). Yields, specific rotations, enantiomeric excess values, and absolute configurations of the products 10a–e are shown in Table 4. The spectroscopic data are in full agreement with those reported in the literature. Stage 1: With C10H13NO in hexane, toluene, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, T= 0 - 20 °C , Inert atmosphere, Overall yield = 76 percent; enantioselective reaction Rachwalski, Michal; Jarzynski, Szymon; Lesniak, Stanislaw; Tetrahedron Asymmetry; vol. 24; nb. 7; (2013); p. 421 - 425 View in Reaxys 4.3 Asymmetric addition of diethylzinc to aldehydes—general procedure General procedure: Chiral catalysts 8a–b or 9a–c (0.1mmol) in dry toluene (5mL) were placed in a round-bottomed flask. The mixture was cooled to 0°C and a solution of diethylzinc (1.0M solution in hexane, 3mmol) was then added under argon. After stirring for 30min, an aldehyde (1mmol) was added at 0°C and the mixture was stirred at room temperature overnight. Next, 5percent aqueous solution of HCl was added, the layers were separated and the aqueous phase was extracted with diethyl ether (4×). The combined organic layers were washed with brine (10mL) and dried over anhydrous MgSO4. The solvents were evaporated to afford the crude alcohols 10a–e, which were purified via column chromatography on silica gel (ethyl acetate with hexane in gradient). Yields, specific rotations, enantiomeric excess values, and absolute configurations of the products 10a–e are shown in Table 4. The spectroscopic data are in full agreement with those reported in the literature. Stage 1: With C12H17NO in hexane, toluene, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, T= 0 - 20 °C , Inert atmosphere, Overall yield = 82 percent; enantioselective reaction Rachwalski, Michal; Jarzynski, Szymon; Lesniak, Stanislaw; Tetrahedron Asymmetry; vol. 24; nb. 7; (2013); p. 421 - 425 View in Reaxys 1 : 3.2 General procedure for asymmetric alkylation using diethylzinc General procedure: To a mixture of catalyst (0.2mmol) and solvent (0.75mL) was added diethylzinc (5.0mmol) slowly at −20°C and stirred for 30min at 0°C. After that, aldehyde (1.0mmol) in solvent (0.25mL) was added at −40°C and stirred for 48h at −20°C. The reaction was quenched by addition of 1N HCl aq and extracted with diethyl ether. The combined organic layers were dried over Na2SO4, and evaporated. The residue was purified by silica gel column chromatography (eluent: hexane/ethyl acetate=3/1). Stage 1: With methyl 2,3-di-O-methyl-η-D-glucopyranoside in hexane, Time= 0.5h, T= -20 - 0 °C , Inert atmosphere, Schlenk technique Stage 2: in hexane, Time= 48h, T= -40 - -20 °C , Inert atmosphere, Schlenk technique, Reagent/catalyst, Overall yield = 55 percent; enantioselective reaction Michigami, Kyosuke; Hayashi, Masahiko; Tetrahedron; vol. 69; nb. 21; (2013); p. 4221 - 4225 View in Reaxys 1 : 3.2 General procedure for asymmetric alkylation using diethylzinc General procedure: To a mixture of catalyst (0.2mmol) and solvent (0.75mL) was added diethylzinc (5.0mmol) slowly at −20°C and stirred for 30min at 0°C. After that, aldehyde (1.0mmol) in solvent (0.25mL) was added at −40°C and stirred for 48h at −20°C. The reaction was quenched by addition of 1N HCl aq and extracted with diethyl ether. The combined organic layers were dried over Na2SO4, and evaporated. The residue was purified by silica gel column chromatography (eluent: hexane/ethyl acetate=3/1). Stage 1: With methyl 2,3-di-O-methyl-η-D-glucopyranoside in hexane, Time= 0.5h, T= -20 - 0 °C , Inert atmosphere, Schlenk technique Stage 2: in hexane, Time= 48h, T= -40 - -20 °C , Inert atmosphere, Schlenk technique, Reagent/catalyst, Overall yield = 63 percent; enantioselective reaction Michigami, Kyosuke; Hayashi, Masahiko; Tetrahedron; vol. 69; nb. 21; (2013); p. 4221 - 4225 View in Reaxys 4.10. General procedure for the reactions of benzaldehyde with diethylzinc in the presence of chiral catalyst 7, 9, 10, or 12–30 General procedure: To the respective catalyst (0.1mmol) 7, 9, 10, or 12–30, a 1M solution of Et2Zn in n-hexane (3mL, 3mmol) was added under an Ar atmosphere at room temperature. The reaction mixture was stirred for 25min at room temperature, and then benzaldehyde (0.10g, 1mmol) was added, followed by stirring at room temperature for a further 20h. The reaction was quenched with saturated NH4Cl solution (15mL) and the mixture was extracted with EtOAc (2×20mL). The combined organic

95/258

2018-07-03 17:29:03

phase was washed with H2O (10mL), dried (Na2SO4), and evaporated under vacuum. The crude secondary alcohols obtained were purified by flash column chromatography on silica gel (n-hexane/EtOAc=4:1). The enantiomeric excess and absolute configuration of the resulting material were determined by chiral GC, using a chiral stationary phase (Chirasil-Dex CB column) at 90°C for 1-phenyl-1-propanol 32 and 33 [tR1=23.2min for the (S)-isomer, tR2=24.1min for the (R)-isomer].9 The sign of the specific rotation of each product was also measured. Stage 1: With (1R,2R,3S,5R)-N,6,6-trimethyl-2-(4-methylphenylsulfonamido)-N-phenylbicyclo[3.1.1]heptane-3-carboxamide in hexane, Time= 0.416667h, T= 20 °C , Inert atmosphere Stage 2: in hexane, Time= 20h, T= 20 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 75 percent; enantioselective reaction Csillag, Kinga; Szakonyi, Zsolt; Fueloep, Ferenc; Tetrahedron Asymmetry; vol. 24; nb. 9-10; (2013); p. 553 - 561 View in Reaxys 4.10. General procedure for the reactions of benzaldehyde with diethylzinc in the presence of chiral catalyst 7, 9, 10, or 12–30 General procedure: To the respective catalyst (0.1mmol) 7, 9, 10, or 12–30, a 1M solution of Et2Zn in n-hexane (3mL, 3mmol) was added under an Ar atmosphere at room temperature. The reaction mixture was stirred for 25min at room temperature, and then benzaldehyde (0.10g, 1mmol) was added, followed by stirring at room temperature for a further 20h. The reaction was quenched with saturated NH4Cl solution (15mL) and the mixture was extracted with EtOAc (2×20mL). The combined organic phase was washed with H2O (10mL), dried (Na2SO4), and evaporated under vacuum. The crude secondary alcohols obtained were purified by flash column chromatography on silica gel (n-hexane/EtOAc=4:1). The enantiomeric excess and absolute configuration of the resulting material were determined by chiral GC, using a chiral stationary phase (Chirasil-Dex CB column) at 90°C for 1-phenyl-1-propanol 32 and 33 [tR1=23.2min for the (S)-isomer, tR2=24.1min for the (R)-isomer].9 The sign of the specific rotation of each product was also measured. Stage 1: With (1R,2R,3S,5R)-6,6-dimethyl-2-(4-methylphenylsulfonamido)-N-phenylbicyclo[3.1.1]heptane-3-carboxamide in hexane, Time= 0.416667h, T= 20 °C , Inert atmosphere Stage 2: in hexane, Time= 20h, T= 20 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 90 percent; enantioselective reaction Csillag, Kinga; Szakonyi, Zsolt; Fueloep, Ferenc; Tetrahedron Asymmetry; vol. 24; nb. 9-10; (2013); p. 553 - 561 View in Reaxys Asymmetric addition of diethylzinc to aldehydes—general procedure General procedure: Chiral catalysts of type 5 (0.1mmol) in dry toluene (5mL) were placed in a round-bottomed flask. The mixture was cooled to 0°C and a solution of diethylzinc (1.0M soln in hexane, 3.0mmol) was added under argon. After stirring for 30min, an aldehyde (1.0mmol) was added at 0°C, and the mixture was stirred at room temperature overnight. Next, 5percent HCl aqueous solution was added, and the layers were separated after which the aqueous phase was extracted with diethyl ether (4×10mL). The combined organic layers were washed with brine (10mL) and dried over anhydrous MgSO4. The solvents were evaporated to afford the crude alcohols 6a–e, which were purified via column chromatography on silica gel (hexane with ethyl acetate in gradient). The yields, specific rotations, enantiomeric excess values, and the absolute configurations of the products 6a–e are shown in Table 4. The spectroscopic data are in full agreement with those reported in the literature. Stage 1: With (S)-2-(2,2-dimethylaziridin-1-yl)-1-phenylethanol in hexane, toluene, Time= 30h, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, T= 0 - 20 °C , Overall yield = 62 percent; enantioselective reaction Rachwalski, Michal; Jarzynski, Szymon; Jasinski, Marcin; Lesniak, Stanislaw; Tetrahedron Asymmetry; vol. 24; nb. 11; (2013); p. 689 - 693 View in Reaxys Representative procedure for the addition of Et2Zn to aldehyde General procedure: To a stirred solution of pyridylsulfinamide ligand 2a (0.057 g, 0.2 mmol) in dry toluene (2 mL) was added diethylzinc (1.1 M solution in toluene, 1.4 mL, 1.51 mmol) at 0 °C dropwise and stirred for 15 min at 0 °C. Aldehyde (0.12 mL, 1.0 mmol) was added into the reaction mixture at 0 °C and reaction mixture was warmed slowly to rt and stirred at rt until the completion of the reaction. After completion of the reaction, it was quenched by the addition of satd NH4Cl solution (10 mL) and the mixture was extracted with EtoAc (15 mL×2). The combined organic layers were washed with brine (20 mL), dried over Na2SO4, and concentrated in vacuo. The residue was purified by silica gel column chromatography using EtoAc/hexane mixture as eluent to give the product alcohols. 4.1.16 (S)-1-Phenylpropan-1-ol (4) (0032) Yield 88percent, er (S:R) 94.6:5.4. Enantiomeric ratio was determined by chiral HPLC analysis (CHIRALCEL OD-H, 2.5percent IPA in hexane, 0.5 mL/min, 254 nm UV detector). tR=15.19 min for (R) and tR=17.13 min for (S). [η]D 24 −39.8 (c 1.0, CHCl3); 1H NMR (400 MHz, CDCl3) H η 7.42–7.27 (m,

96/258

2018-07-03 17:29:03

5H), 4.58 (t, J=6.4 Hz, 1H), 2.11 (br s, 1H), 1.91–1.66 (m, 2H), 0.92 (t, J=7.6 Hz, 3H); 13C NMR (100 MHz, CDCl3) ηC 144.5, 128.3 (2C), 127.4, 125.9 (2C), 75.9, 31.8, 10.1. Stage 1: With (S)-2-methyl-N-((S)-phenyl(pyridin-2-yl)methyl)propane-2-sulfinamide in toluene, Time= 0.25h, T= 0 °C Stage 2: in toluene, Time= 4h, T= 0 - 20 °C , Reagent/catalyst, Time, Overall yield = 88 percent; enantioselective reaction Prasad, Kavirayani R.; Revu, Omkar; Tetrahedron; vol. 69; nb. 39; (2013); p. 8422 - 8428 View in Reaxys 2.3.1. General procedure for the asymmetric addition ofdiethylzinc to aldehydes catalyzed by PS catalysts General procedure: To a stirred suspension of the polymer-supported catalyst(10 molpercent) in toluene (1 mL) was added a solution of aldehyde inhexanes under argon, and the stirring was continued at r.t. for30 min. After the addition of diethylzinc (1.1 M in toluene) at 0 C,the reaction mixture was stirred at r.t. for a further 36 h, and wasthen quenched with 1 M HCl (4 mL). The resulting mixture was filteredand the filtrate was extracted with CH2Cl2 (3×10 mL). Thecombined organic layers were dried with anhydrous MgSO4 andconcentrated under reduced pressure. Purification of the residueby flash chromatography (PE/ AcOEt 15:1) afforded the desired alcohol.The enantiomeric excess and the absolute configuration of theresulting alcohols were determined by HPLC and optical rotation.The catalyst was collected by filtration, washed with dry CH2Cl2,vacuum dried and used for a new run. For regeneration, the polymerwas stirred with 1 M HCl-THF (1:2 mL) for 1 h, and then washedsuccessively with CH2Cl2 (3×15 mL), THF (2×15 mL) and MeOH(2×15 mL). After vacuum dried at 50 C for 5 h, the resin could bereused in the successive catalytic reactions. A typical analysis ofthe reaction products separated reveals (R)- and (S)-1-phenyl-1-propanol (12), and a small amount of benzyl alcohol (13), as theside-product. The selectivity was calculated by the following equationbased on the 1H NMR peak areas:Selectivity= 1212+13×100. With polymer supported amide of L-phenylalanine in toluene, Time= 36h, T= 25 °C , Catalytic behavior, Temperature, Solvent, Optical yield = 71 percent ee; enantioselective reaction Escorihuela, Jorge; Gonzalez, Laura; Altava, Belen; Burguete, M. Isabel; Luis, Santiago V.; Applied Catalysis A: General; vol. 462-463; (2013); p. 23 - 30 View in Reaxys Stage 1: With (1'R,2R,3R)-1-(1'-phenylethyl)-2-phenyl-3-hydroxyazetidine in toluene, Time= 0.333333h, T= 20 °C Stage 2: in toluene, Time= 29h, T= 20 °C , Inert atmosphere, Overall yield = 36 percent; enantioselective reaction Zhang, Zhanbin; Li, Min; Zi, Guofu; Chirality; vol. 19; nb. 10; (2007); p. 802 - 808 View in Reaxys With titanium(IV) isopropylate in toluene, T= -25 - -20 °C , Inert atmosphere, Overall yield = 90 percent; Overall yield = 1.36 g; enantioselective reaction Comina, Paul J.; Beck, Albert K.; Seebach, Dieter; Organic Process Research and Development; vol. 2; nb. 1; (1998); p. 18 26 View in Reaxys 4.4 General procedure for enantioselective addition of diethylzinc to aldehydes General procedure: To a solution of the corresponding ligand 9a, 11a, 14a, 16a, and 17a (3molpercent) in 4ml of toluene, Et2Zn (2.22mmol of 1M solution in hexane) was added dropwise at 0°C. The mixture was stirred for 30min at 0°C and then the corresponding aldehyde (1.30mmol) was added at −25°C. The reaction was stirred at rt and monitored by TLC (hexane/MTBE=2:1) until the aldehyde was consumed. The mixture was quenched (aq. NH4Cl), extracted with Et2O (3×20ml), and dried. After evaporation of the solvent, the crude product was purified by column chromatography (hexane/MTBE=5:1). The enantiomeric excess of the products was determinated by HPLC or GC with chiral columns. Stage 1: With 1-((S)-naphthalen-1-yl((S)-1-phenylethylamino)methyl)naphthalene-2,6-diol in hexane, toluene, Time= 0.5h, T= 0 °C , Schlenk technique, Inert atmosphere Stage 2: in hexane, toluene, Time= 144h, T= -25 - 20 °C , Schlenk technique, Inert atmosphere, Reagent/catalyst, Overall yield = 88 percent; enantioselective reaction Marinova, Maya; Kostova, Kalina; Tzvetkova, Pavleta; Tavlinova-Kirilova, Maya; Chimov, Angel; Nikolova, Rosica; Shivachev, Boris; Dimitrov, Vladimir; Tetrahedron Asymmetry; vol. 24; nb. 23; (2013); p. 1453 - 1466 View in Reaxys Stage 1: With 1-butyl-3-[[[(1S)-1-(hydroxymethyl)-2-methylpropyl]methylamino]methyl]pyridinium bis(trifluoromethanesulfonyl)imide, 1-butyl-2,3-dimethylimidazolium bis-(trifluoromethanesulfonyl)amide in hexane, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, Time= 48h, T= 20 °C , Inert atmosphere

97/258

2018-07-03 17:29:03

Stage 3: With hydrogenchloride in hexane, water, Inert atmosphere, Reagent/catalyst, Overall yield = 59 percent; enantioselective reaction Vasiloiu, Maria; Leder, Sonja; Gaertner, Peter; Mereiter, Kurt; Bica, Katharina; Organic and Biomolecular Chemistry; vol. 11; nb. 46; (2013); p. 8092 - 8102 View in Reaxys Stage 1: With 1-butyl-3-[[[2-hydroxy-1-methyl-2-phenylethyl]-methylamino]methyl]pyridinium bis(trifluoromethanesulfonyl)imide in hexane, dichloromethane, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, dichloromethane, Time= 48h, T= 20 °C , Inert atmosphere Stage 3: With hydrogenchloride in hexane, dichloromethane, water, Inert atmosphere, Reagent/catalyst, Overall yield = 81 percent; enantioselective reaction Vasiloiu, Maria; Leder, Sonja; Gaertner, Peter; Mereiter, Kurt; Bica, Katharina; Organic and Biomolecular Chemistry; vol. 11; nb. 46; (2013); p. 8092 - 8102 View in Reaxys Stage 1: With (diphenylphosphoryl)[(R)-[(2R,4S,5R)-5-ethenyl-1-azabicyclo[2.2.2]octan-2-yl](6-methoxyquinolin-4-yl)methyl]amine in tetrahydrofuran, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in tetrahydrofuran, Time= 6h, T= 0 - 20 °C , Inert atmosphere, Concentration, Reagent/catalyst, Solvent, Temperature, Overall yield = 84 percent; enantioselective reaction Shen, Bin; Huang, Huayin; Bian, Guangling; Zong, Hua; Song, Ling; Chirality; vol. 25; nb. 9; (2013); p. 561 - 566 View in Reaxys Stage 1: With (diphenylphosphoryl)[(S)-[(2S,4S,5R)-5-ethenyl-1-azabicyclo[2.2.2]octan-2-yl](quinolin-4-yl)methyl]amine in dichloromethane, toluene, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in dichloromethane, toluene, Time= 6h, T= 0 - 20 °C , Inert atmosphere, Concentration, Reagent/catalyst, Solvent, Temperature, Overall yield = 72 percent; enantioselective reaction Shen, Bin; Huang, Huayin; Bian, Guangling; Zong, Hua; Song, Ling; Chirality; vol. 25; nb. 9; (2013); p. 561 - 566 View in Reaxys General procedure: addition of Et2Zn to benzaldehyde To a solution of ligands 4–19 (0.0294 mmol, 3 mol percent) in dry toluene(5.0 ml) under an argon atmosphere at 10 C was slowlyadded Et2Zn (1.0 M in hexane, 1.5 ml, 1.5 mmol). The resultingsolution was stirred at this temperature for 1 h, then cooled to20 C and benzaldehyde (0.1 ml, 0.104 g, 0.98 mmol) was added.The reaction mixture was warmed to room temperature and stirredfor the appropriate time (TLC monitoring), (see Table 3). Nextthe reaction mixture was quenched with 8 mL of aqueous saturatedsolution of NH4Cl and then filtered through Celite. Afterextraction with Et2O, the organic layer was dried over anhydrousNa2SO4, evaporated and the residue was chromatographed to affordpure 1-phenyl-1-propanol. The enantiomeric excess and theabsolute configuration of the resulting alcohol were determinedby chiral GC for determining the asymmetric induction reached(ee and major enantiomer). Stage 1: With (1S,2R,4R)-1-((R)-2-(diisopropylamino)-1-hydroxyethyl)-7,7-dimethylbicyclo[2.2.1]heptan-2-ol in hexane, toluene, Time= 1h, T= -10 °C , Inert atmosphere Stage 2: in hexane, toluene, Time= 65h, T= -20 - 20 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 96 percent; enantioselective reaction Stoyanova, Malinka P.; Shivachev, Boris L.; Nikolova, Rosica P.; Dimitrov, Vladimir; Tetrahedron Asymmetry; vol. 24; nb. 21-22; (2013); p. 1426 - 1434 View in Reaxys 4.3 Asymmetric addition of diethylzinc to aldehydes; general procedure11 General procedure: The chiral catalyst of type 5 (0.1mmol) in dry toluene (5mL) was placed in a round-bottomed flask. The mixture was cooled to 0°C and a solution of diethylzinc (1.0M in hexane, 3.0mmol) was added under argon. After stirring for 30min, an aldehyde (1.0mmol) was added at 0°C, and the mixture was stirred at room temperature overnight. Next, a 5percent HCl aqueous solution was added, the layers were separated and the aqueous phase was extracted with diethyl ether (4×10mL). The combined organic layers were washed with brine (10mL) and dried over anhydrous MgSO4. The solvents were evaporated off to afford the crude alcohols 6a–e, which were purified via column chromatography on silica gel (eluting with hexane with ethyl acetate in gradient). The yields, specific rotations, enantiomeric excess values, and the absolute configurations of products 6a–e are collected in Table 4. The spectroscopic data are in full agreement with those reported in the literature.7,11,12,21 Stage 1: With C6H13NO in hexane, toluene, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, T= 0 - 20 °C , Reagent/catalyst, Overall yield = 83 percent; enantioselective reaction

98/258

2018-07-03 17:29:03

Lesniak, Stanislaw; Rachwalski, Michal; Jarzynski, Szymon; Obijalska, Emilia; Tetrahedron Asymmetry; vol. 24; nb. 20; (2013); p. 1336 - 1340 View in Reaxys 4.3 Asymmetric addition of diethylzinc to aldehydes; general procedure11 General procedure: The chiral catalyst of type 5 (0.1mmol) in dry toluene (5mL) was placed in a round-bottomed flask. The mixture was cooled to 0°C and a solution of diethylzinc (1.0M in hexane, 3.0mmol) was added under argon. After stirring for 30min, an aldehyde (1.0mmol) was added at 0°C, and the mixture was stirred at room temperature overnight. Next, a 5percent HCl aqueous solution was added, the layers were separated and the aqueous phase was extracted with diethyl ether (4×10mL). The combined organic layers were washed with brine (10mL) and dried over anhydrous MgSO4. The solvents were evaporated off to afford the crude alcohols 6a–e, which were purified via column chromatography on silica gel (eluting with hexane with ethyl acetate in gradient). The yields, specific rotations, enantiomeric excess values, and the absolute configurations of products 6a–e are collected in Table 4. The spectroscopic data are in full agreement with those reported in the literature.7,11,12,21 Stage 1: With C8H17NO in hexane, toluene, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, T= 0 - 20 °C , Overall yield = 87 percent; enantioselective reaction Lesniak, Stanislaw; Rachwalski, Michal; Jarzynski, Szymon; Obijalska, Emilia; Tetrahedron Asymmetry; vol. 24; nb. 20; (2013); p. 1336 - 1340 View in Reaxys With C27H30N4O2 in toluene, Overall yield = 92 percent; enantioselective reaction Lesniak, Stanislaw; Pieczonka, Adam M.; Jarzynski, Szymon; Justyna, Katarzyna; Rachwalski, Michal; Tetrahedron Asymmetry; vol. 24; nb. 20; (2013); p. 1341 - 1344 View in Reaxys With [(1R,2R)-2-(dimethylamino)-1,2-diphenylethyl]({[(1R,2R)-2-(dimethylamino)-1,2-diphenylethyl]amino}(phenyl)thiophosphoryl)amine in toluene, Time= 6h, T= 0 - 20 °C , Inert atmosphere, Temperature, Overall yield = 84 percent Yue, Huifeng; Huang, Huayin; Bian, Guangling; Zong, Hua; Li, Fangling; Song, Ling; Tetrahedron Asymmetry; vol. 25; nb. 2; (2014); p. 170 - 180 View in Reaxys With tert-butyl N-[(1R,2R)-2-[({[(1R,2R)-2-{[(tert-butoxy)carbonyl]amino}-1,2-diphenylethyl]amino}(phenyl)thiophosphoryl)amino]-1,2-diphenylethyl]carbamate in toluene, Time= 6h, T= 0 - 20 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 98 percent Yue, Huifeng; Huang, Huayin; Bian, Guangling; Zong, Hua; Li, Fangling; Song, Ling; Tetrahedron Asymmetry; vol. 25; nb. 2; (2014); p. 170 - 180 View in Reaxys General procedure for the enantioselective addition of diethylzinc to aldehydes using 31 or 35 as the chiral ligand General procedure: Using 35 as the chiral ligand; To a solution of 35 (41.5mg, 0.05mmol) in hexane (0.75mL), diethylzinc (0.75mL of 1.0M solution in hexane, 0.75mmol) was slowly added at 0°C under a nitrogen atmosphere and stirred for 30min. Next, the aldehyde (0.5mmol) was added dropwise. The mixture was stirred for 10min at 0°C and then stirred for 50min at room temperature. The solution was then quenched with saturated aqueous HCl (10percent, 10mL). Extraction with EtOAc gave combined organic layers that were washed with brine, dried over Na2SO4, and concentrated in vacuo to give a residue which was subjected to silica gel column chromatography, to afford the corresponding secondary alcohol (S)-37. The ee value and absolute configuration were determined by comparing Chiral GC Chirasil Dex CB analysis tR and the specific rotation with the literature data.11,29 Stage 1: With benzyl N-[(1R,2R)-2-[({[(1R,2R)-2-{[(benzyloxy)carbonyl]amino}-1,2-diphenyl ethyl]amino}(phenyl)thiophosphoryl)amino]-1,2-diphenylethyl]carbamate in hexane, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, Time= 1h, T= 20 °C , Inert atmosphere, Solvent, Temperature, Overall yield = 85 percent; enantioselective reaction Yue, Huifeng; Huang, Huayin; Bian, Guangling; Zong, Hua; Li, Fangling; Song, Ling; Tetrahedron Asymmetry; vol. 25; nb. 2; (2014); p. 170 - 180 View in Reaxys General procedure for Carbene-Catalyzed diethylzinc addition to benzldehydes To a solution of the chiral imidazolinium chloride 1 (0.05m mol) in dry toluene (5 ml) was added KO-tBu(0.05 mmol) under N2 atmosphere. The solution was stirred for 5 minat room temperature before cooling down to -10 C. At this temperature (1.1mmol)

99/258

2018-07-03 17:29:03

Et2Zn-solution (1M in hexane) was added, and after 5 min,benzaldehyde (0.50 mmol) was added. The mixture was stirred for 15 h, quenched by the addition of 1 M HCl (1 mL), and extracted with Et2O (15 mL).The combined extracts were dried over MgSO4. The organic phase was concentrated under reduced pressure and the crude product was purified by silica gel column chromatography (eluent: hexane/EtOAc), to give the corresponding alcohol 9. [η]D 20 = -14.1 (c = 3.5,CHCl3). 1H NMR (300MHz, CDCl3) η = 0.88 (t, J= 7.3 Hz, 3H), 1.63-1.81 (m, 2H), 4.52 (t, J = 6.6Hz, 1H), 7.38-7.45 (m,5H) ppm. 13C NMR (75.46 MHz, CDCl3) η = 9.9, 31.9, 75.2,126.6, 127.4, 128.5, 143.0. The enantiomeric excess was determined by HPLC using a Chiralcel OD column (3percent isopropanol in hexanes, flow 1.0 mL/min); t1(R)= 11.3 min, t2(S) = 14.3 min, (maximum ee = 33percent (S))]. With magnesia, (S)-1-benzyl-3-((S)-1-hydroxy-3-phenylpropan-2-yl)-5-isobutyl-4,5-dihydro-1H-imidazol-3-ium chloride, potassium tert-butylate in hexane, toluene, Time= 15.1667h, T= -10 - 20 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 95 percent; Optical yield = 33 percent ee Faraji, Laleh; Jadidi, Khosrow; Notash, Behrouz; Tetrahedron Letters; vol. 55; nb. 2; (2014); p. 346 - 350 View in Reaxys 1 Stage 1: With 2,2'-(propane-2,2-diyl)bis(6,6-dimethyl-5,6,7,8-tetrahydro-5,7-methanoquinoline-8,2-diyl)bis(diphenylmethanol) in tetrahydrofuran, T= 20 °C , Inert atmosphere Stage 2: in tetrahydrofuran, Time= 24h, T= 20 °C , Inert atmosphere, Catalytic behavior, Reagent/catalyst, Concentration, Solvent, Overall yield = 31 percent; enantioselective reaction Shih, Yi-Shan; Boobalan, Ramalingam; Chen, Chinpiao; Lee, Gene-Hsian; Tetrahedron Asymmetry; vol. 25; nb. 4; (2014); p. 327 - 333 View in Reaxys 4.3. Asymmetric addition of diethylzinc to aldehydes; generalprocedure General procedure: Chiral catalysts of type 4 (0.1 mmol) in dry toluene (5 mL) were placed in a round-bottomed flask. The mixture was cooled to 0 °C and a solution of diethylzinc (1.0 M sln. in hexane, 3.0 mmol) was added under argon. After stirring for 30 min, an aldehyde (1.0 mmol) was added at 0°C, and the mixture was stirred at room temperature overnight. Next, a 5percent HCl aqueous solution was added, the layers were separated, and the aqueous phase was extracted with diethyl ether (4×10 mL). The combined organic layers were washed with brine (10 mL) and dried over anhydrous MgSO4. The solvents were evaporated off to afford the crude alcohols 5a–e, which were purified via column chromatography on silica gel (hexane with ethyl acetate in gradient). The yields, specific rotations, enantiomeric excess values, and the absolute configurations of products 5a–e are collected in Table 3. The spectroscopic data were in full agreement with those reported in the literature. Stage 1: With C15H27NO in hexane, toluene, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, T= 0 - 20 °C , Inert atmosphere, Overall yield = 91 percent; enantioselective reaction Rachwalski, Michal; Tetrahedron Asymmetry; vol. 25; nb. 3; (2014); p. 219 - 223 View in Reaxys A typical asymmetric addition reaction of diethylzinc with aldehydes induced by chiral amino diol tridentate ligands A flask flushed with argon was charged with 10 mL of tolueneand chiral amino diol tridentate ligand. To the flask was addedTi(O-i-Pr)4 under an argon stream. The mixture was then stirredat room temperature for 1 h. Next, 3 mL of the solution of diethylzincin n-hexane was added dropwise and the mixture wasstirred for 1 h. 1 mmol of the aldehyde was added at 0 C andthe reaction mixture was stirred at 0 C for several hours afterthe addition of aldehyde. The reaction was quenched withhydrochloric acid (1 mol/L). The organic layer was separatedand the aqueous layer was extracted with diethyl ether. The organiclayer and ether extraction were combined, dried overanhydrous MgSO4, and concentrated under reduced pressure.The concentrated residue was purified by chromatography onsilica gel to obtain the product. The ee of the product was determinedby chiral HPLC. Stage 1: With titanium(IV) isopropylate, benzyl bis(3-triphenylmethyl-2-hydroxypropyl)amine in hexane, toluene, Time= 1h, Inert atmosphere Stage 2: in hexane, toluene, T= 0 °C , Inert atmosphere, Overall yield = 83 percent; enantioselective reaction Zhang, An-Lin; Yang, Li-Wen; Yang, Nian-Fa; Liu, Yan-Ling; Tetrahedron Asymmetry; vol. 25; nb. 4; (2014); p. 289 - 297 View in Reaxys A typical asymmetric addition reaction of diethylzinc with aldehydes induced by chiral amino diol tridentate ligands A flask flushed with argon was charged with 10 mL of tolueneand chiral amino diol tridentate ligand. To the flask was addedTi(O-i-Pr)4 under an argon stream. The mixture was then stirredat room temperature for 1 h. Next, 3 mL of the solution of diethylzincin n-hexane was added dropwise and the mixture wasstirred for 1 h. 1 mmol of the aldehyde was added at 0 C andthe

100/258

2018-07-03 17:29:03

reaction mixture was stirred at 0 C for several hours afterthe addition of aldehyde. The reaction was quenched withhydrochloric acid (1 mol/L). The organic layer was separatedand the aqueous layer was extracted with diethyl ether. The organiclayer and ether extraction were combined, dried overanhydrous MgSO4, and concentrated under reduced pressure.The concentrated residue was purified by chromatography onsilica gel to obtain the product. The ee of the product was determinedby chiral HPLC. Stage 1: With titanium(IV) isopropylate, benzyl bis[3-(9-ethylfluoren-9-yl)-2(S)-hydroxypropyl]amine in hexane, toluene, Time= 1h, Inert atmosphere Stage 2: in hexane, toluene, T= 0 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 77 percent; enantioselective reaction Zhang, An-Lin; Yang, Li-Wen; Yang, Nian-Fa; Liu, Yan-Ling; Tetrahedron Asymmetry; vol. 25; nb. 4; (2014); p. 289 - 297 View in Reaxys General procedure for the enantioselective diethylzinc addition to aromaticaldehydes General procedure: Under an argon atmosphere, chiral ligand 3 or 4 (0.025 mmol)was dissolved in dry solvent and Ti(OiPr)4 (0.23 mmol) was added and themixture stirred for 1 h. Et2Zn (0.5 mmol, 1 M in hexane) was added and theresulting yellow solution was stirred for 20 min at room temperature. Themixture was cooled to 0 C and the aromatic aldehyde was added (0.25 mmol).The mixture was stirred for another 24 h. After quenching with saturatedNH4Cl solution (1 mL), H2O (25 mL) was added and the mixture extracted withEtOAc (3 25 mL). The combined organic phases were dried over Na2SO4 andevaporated in vacuo. The crude product was purified by flash chromatographyto give the corresponding alcohol. Enantiomeric excesses were determined byHPLC analysis with a chiral stationary phase column (Chiralcel OD-H orChiralcel OB). Stage 1: With titanium(IV) isopropylate, (1R,2R)-1,2-bis(3,5-dibromophenyl)ethane-1,2-diol in hexane, dichloromethane, Time= 0.333333h, T= 25 °C , Inert atmosphere Stage 2: in hexane, dichloromethane, Time= 24h, T= 0 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 56 percent; Optical yield = 32 percent ee; enantioselective reaction Goek, Yasar; Kekec, Levent; Tetrahedron Letters; vol. 55; nb. 16; (2014); p. 2727 - 2729 View in Reaxys With (1R,2R)-1,2-bis([1,1’:3’,1’’-terphenyl]-5’-yl)ethane-1,2-diol in toluene, Time= 24h, T= 25 °C , Catalytic behavior, Solvent, Overall yield = 38 percent; Optical yield = 79percent ee; enantioselective reaction Goek, Yasar; Kekec, Levent; Tetrahedron Letters; vol. 55; nb. 16; (2014); p. 2727 - 2729 View in Reaxys General Procedure for CPOP/Ti-Catalyzed Diethylzinc Addition Reactions. To a dry sample of CPOP-1 (13.2 mg, 0.02mmol) in 1mL of dry toluene was added Ti(OiPr)4 (85 mg, 0.3mmol), and the resulting mixture was stirred for 1 h. The solvent was evaporated under reduced pressure to remove i-PrOH and about 0.5 mL of toluene. The reaction mixture was cooled to 78 °C. Benzaldehyde (10.6 mg, 0.1mmol) in Et2O (0.5 mL) and diethylzinc in toluene (400 L, 1.0 M, 0.4 mmol) were then added sequentially to the stirring suspension and allowed to react for 10 h from 78 °C to room temperature. The reaction mixture was quenched by the addition of 1 mL of 1M HCl. The organic layer was analyzed by 1H NMR and HPLC to give conversion and ee seperately. With titanium(IV) isopropylate in toluene, Time= 10h, T= -78 - 20 °C , Catalytic behavior, Reagent/catalyst, Solvent, Temperature, enantioselective reaction Wang, Xiuren; Zhang, Jie; Liu, Yan; Cui, Yong; Bulletin of the Chemical Society of Japan; vol. 87; nb. 3; (2014); p. 435 440 View in Reaxys 99 %Chromat.

Stage 1: With tetradecane, (EtZn)3(THF)2(1,1η-bi-2-naphtholate)3Eu(THF), Triphenylphosphine oxide in toluene, Time= 0.5h, T= 20 °C , Inert atmosphere, Sealed tube Stage 2: in toluene, Time= 48h, Inert atmosphere, Sealed tube, Catalytic behavior, Reagent/catalyst, Concentration, enantioselective reaction Nieto, Ismael; Wooten, Alfred J.; Robinson, Jerome R.; Carroll, Patrick J.; Schelter, Eric J.; Walsh, Patrick J.; Organometallics; vol. 32; nb. 24; (2013); p. 7431 - 7439 View in Reaxys

98 %Chromat.

Stage 1: With tetradecane, [Li3(THF)4][(1,1η-bi-2-naphtholate)3Eu(THF)] in toluene, Time= 0.5h, T= 20 °C , Inert atmosphere, Sealed tube Stage 2: in toluene, Time= 24h, Sealed tube, Inert atmosphere, Catalytic behavior, Reagent/catalyst, Concentration, enantioselective reaction

101/258

2018-07-03 17:29:03

Nieto, Ismael; Wooten, Alfred J.; Robinson, Jerome R.; Carroll, Patrick J.; Schelter, Eric J.; Walsh, Patrick J.; Organometallics; vol. 32; nb. 24; (2013); p. 7431 - 7439 View in Reaxys Stage 1: With ethyl (4S,10aR)-2-methyl-5-oxo-4-(2-thienyl)-1,4,5,7,8,9,-10,10a-octahydropyrido[2',3':3,4]pyrrolo[1,2-a]pyrimidine-3-carboxylate in hexane, toluene, Time= 0.25h, T= 20 °C Stage 2: in hexane, toluene, Time= 24h, T= 0 - 20 °C , Reagent/catalyst Marchalin, Stefan; Valigura, Dusan; Varecka, Ludovit; Lakatos, Boris; Vanekova, Monika; Baran, Peter; Lawson, Ata Martin; Daich, Adam; Monatshefte fur Chemie; vol. 145; nb. 5; (2014); p. 835 - 847 View in Reaxys 4.6 General procedure for the catalytic asymmetric addition of Et2Zn to aldehydes General procedure: Ligand 1c (0.188mmol) was dissolved in toluene (2mL) and Et2Zn (2M in toluene, 2.26mmol) was added in one portion after which the reaction was stirred for 45min. at ambient temperature. The mixture was then cooled to −20°C and the aldehyde (1.88mmol) was added as dissolved in toluene (2mL) into the reaction. The resulting mixture was stirred for 24h at −20°C. The reaction was quenched with saturated ammonium chloride (10mL) and extracted with ethyl acetate (3×10mL). The combined organic extracts were dried over Na2SO4 and concentrated. Purification of the crude product was carried out by micro distillation under reduced pressure. The product was subjected to HPLC by using Chiralcel OD-H column and GC by using Supelco η-Dex capillary column to determine the ee values. With (S)-3-amino-2-(1-hydroxy-2,2-dimethylprop-1-yl)-quinazolin-4(3H)-one in toluene, Time= 24h, T= -20 °C , Inert atmosphere, Schlenk technique, Temperature, Solvent, Reagent/catalyst, Overall yield = 95 percent Karabuga, Semistan; Karakaya, Idris; Ulukanli, Sabri; Tetrahedron Asymmetry; vol. 25; nb. 10-11; (2014); p. 851 - 855 View in Reaxys With C44H31NO2 in hexane, toluene, Time= 48h, T= -78 - 0 °C , Inert atmosphere, Overall yield = 16 percent; Overall yield = 7.5 mg Zheng, Jun; You, Shu-Li; Chemical Communications; vol. 50; nb. 60; (2014); p. 8204 - 8207 View in Reaxys With titanium(IV) isopropylate, C36H40N4O2 (2+)*2C2F6NO4S2 (1-), Time= 2.5h, T= 25 °C , Inert atmosphere, Ionic liquid, Reagent/catalyst, Temperature, Solvent, Overall yield = 80 percent; enantioselective reaction Vidal, Marc; Schmitzer, Andreea R.; Organometallics; vol. 33; nb. 13; (2014); p. 3328 - 3340 View in Reaxys With titanium(IV) isopropylate, C36H40N4O2 (2+)*2C2F6NO4S2 (1-), Time= 2.5h, T= 25 °C , Inert atmosphere, Ionic liquid, Reagent/catalyst, Overall yield = 67 percent; enantioselective reaction Vidal, Marc; Schmitzer, Andreea R.; Organometallics; vol. 33; nb. 13; (2014); p. 3328 - 3340 View in Reaxys Stage 1: With (2S,2ηR)-2,2η-((pyridine-2,6-diylbis(methylene))bis(azanediyl))bis(4-methyl-1,1-diphenylpentan-1-ol) in hexane, toluene, Time= 2h, T= 20 °C , Inert atmosphere Stage 2: in hexane, toluene, T= 20 °C , Inert atmosphere, Reagent/catalyst, Temperature, Solvent, Overall yield = 84 percent; enantioselective reaction Zhang, Weijie; Tang, Ruiren; Yu, Huirong; Gao, Shu; Applied Organometallic Chemistry; vol. 28; nb. 7; (2014); p. 545 - 551 View in Reaxys Stage 1: With (2S,2ηR)-2,2η-((pyridine-2,6-diylbis(methylene))bis(azanediyl))bis(1,1,2-triphenylethanol) in hexane, toluene, Time= 2h, T= 20 °C , Inert atmosphere Stage 2: in hexane, toluene, T= 20 °C , Inert atmosphere, Overall yield = 82 percent; enantioselective reaction Zhang, Weijie; Tang, Ruiren; Yu, Huirong; Gao, Shu; Applied Organometallic Chemistry; vol. 28; nb. 7; (2014); p. 545 - 551 View in Reaxys General procedure for the reaction of aldehydes with diethylzinc in the presence of chiral catalyst To the respective catalyst (0.1mmol), 1M Et2Zn in n-hexane solution (3mL, 3mmol) was added under an Ar atmosphere at room temperature. The reaction was stirred for 25min at room temperature or 0°C (see Table 3), and benzaldehyde (1mmol) was then added to the solution, with subsequent stirring at room temperature or 0°C (see Table 3) for a further 20h. The reaction was quenched with saturated NH4Cl solution (15mL) and the mixture was extracted with EtOAc (2×20mL). The combined organic

102/258

2018-07-03 17:29:03

phase was washed with H2O (10mL), dried (Na2SO4) and evaporated under vacuum. The crude secondary alcohols obtained were purified by flash column chromatography (n-hexane/EtOAc=4:1). The ee and absolute configuration of the resulting material were determined by chiral GC, using a chiral stationary phase (Chirasil-Dex CB column) at 90°C.40,41 Stage 1: With (1R,2S,3R,5R)-3-hydroxymethyl-6,6-dimethylbicyclo[3.1.1]heptan-2-ol in hexane, Time= 0.416667h, T= 20 °C , Inert atmosphere Stage 2: in hexane, Time= 20h, T= 20 °C , Inert atmosphere, Reagent/catalyst, Solvent, Temperature, Overall yield = 88 percent; enantioselective reaction Szakonyi, Zsolt; Gonda, Tímea; Ötvös, Sándor Balázs; Fülöp, Ferenc; Tetrahedron Asymmetry; vol. 25; nb. 15; (2014); p. 1138 - 1145 View in Reaxys With titanium(IV) isopropylate in toluene, Time= 48h, T= -20 °C , Inert atmosphere, Schlenk technique, Catalytic behavior, Overall yield = 73 percent; enantioselective reaction An, Wan-Kai; Han, Man-Yi; Wang, Chang-An; Yu, Si-Min; Zhang, Yuan; Bai, Shi; Wang, Wei; Chemistry--A European Journal; vol. 20; nb. 35; (2014); p. 11019 - 11028,10 View in Reaxys General procedure for the addition of ZnEt2 to benzaldehyde. The corresponding amount of 1,2-aminoalcohol was suspended in dry toluene (0,5 mL) under argon atmosphere, at 0 °C and a 1.1 M solution of ZnEt2 in hexane (2 mmol) was added. The mixture was stirred at this temperature for 30 min and then, benzaldehyde (1 mmol) was added dropwise. Stirring was continued at 0 °C for 30 min and then at room temperature for 24 h. The reaction was quenched at 0 °C by addition of water. The crude was diluted with ethyl acetate and filtered through a silica column using a sintered glass funnel. The solvent was evaporated under reduced pressure and purified by flash chromatography, allowing the separation of 1-phenyl-1-propanol from the 1,2-aminoalcohol, which could be recover quantitatively and reused. The enantiomeric excess was determined by the use of HPLC (Chiralcel OD) using a mixture hexane - isopropanol (97:3) as the eluent (1 mL / min): (R)-1-phenyl-1-propanol, 9 min; (S)-1-phenyl-1-propanol, 11 min.1-phenyl-1-propanol: Colorless liquid. 1H NMR (300 MHz, CDCl ) η 7.34-7.24 (m, 5 H, arom); 4.48 (t, J1-2= 6.7 Hz, 1 H, H-1); 3.94 (bs, 1 H, OH); 3.78 (m, 2 H, H-2); 3 0.91 (t, J3-2= 7.3 Hz, 3 H, H-3); 13C NMR (75.5 MHz, CDCl3) η 144.4 (C, C-1’); 128.2 (CH, 2C, C-2’ and C-6’); 127.3 (CH, C-4’); 125.8 (CH, 2C, C-3’ and C-5’); 75.8 (CH, C-1); 31.7 (CH2, C-2); 9.9 (CH3, C-3). Stage 1: With C28H33NO4 in hexane, toluene, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, Time= 24.5h, T= 0 - 20 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 77 percent; Optical yield = 66 percent ee Zanardi, Mara M.; Botta, Mara C.; Surez, Alejandra G.; Tetrahedron Letters; vol. 55; nb. 42; (2014); p. 5832 - 5835 View in Reaxys General procedure for the addition of ZnEt2 to benzaldehyde. The corresponding amount of 1,2-aminoalcohol was suspended in dry toluene (0,5 mL) under argon atmosphere, at 0 °C and a 1.1 M solution of ZnEt2 in hexane (2 mmol) was added. The mixture was stirred at this temperature for 30 min and then, benzaldehyde (1 mmol) was added dropwise. Stirring was continued at 0 °C for 30 min and then at room temperature for 24 h. The reaction was quenched at 0 °C by addition of water. The crude was diluted with ethyl acetate and filtered through a silica column using a sintered glass funnel. The solvent was evaporated under reduced pressure and purified by flash chromatography, allowing the separation of 1-phenyl-1-propanol from the 1,2-aminoalcohol, which could be recover quantitatively and reused. The enantiomeric excess was determined by the use of HPLC (Chiralcel OD) using a mixture hexane - isopropanol (97:3) as the eluent (1 mL / min): (R)-1-phenyl-1-propanol, 9 min; (S)-1-phenyl-1-propanol, 11 min.1-phenyl-1-propanol: Colorless liquid. 1H NMR (300 MHz, CDCl ) η 7.34-7.24 (m, 5 H, arom); 4.48 (t, J1-2= 6.7 Hz, 1 H, H-1); 3.94 (bs, 1 H, OH); 3.78 (m, 2 H, H-2); 3 0.91 (t, J3-2= 7.3 Hz, 3 H, H-3); 13C NMR (75.5 MHz, CDCl3) η 144.4 (C, C-1’); 128.2 (CH, 2C, C-2’ and C-6’); 127.3 (CH, C-4’); 125.8 (CH, 2C, C-3’ and C-5’); 75.8 (CH, C-1); 31.7 (CH2, C-2); 9.9 (CH3, C-3). Stage 1: With C21H21NO3 in hexane, toluene, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, Time= 24.5h, T= 0 - 20 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 81 percent Zanardi, Mara M.; Botta, Mara C.; Surez, Alejandra G.; Tetrahedron Letters; vol. 55; nb. 42; (2014); p. 5832 - 5835 View in Reaxys General procedure for the enantioselective addition of diethylzinc to aldehydes using chiral amino alcohol (Sa)-2 General procedure: Ligand (Sa)-2 (0.095 mmol, 4.5 mg, ee 99percent) was dissolved in a solution of diethylzinc (1 M in hexane, 0.6 mmol, 0.6 mL) under nitrogen atmosphere. The mixture was stirred for 1 h at room temperature then cooled to 0 °C. Freshly distilled aldehyde (0.2 mmol) was added to the mixture.The colour of the resulting mixture turned to a distinctive yellow. After

103/258

2018-07-03 17:29:03

stirring for 16 h, the mixture changed to colourless indicating the completion of the reaction. The reaction was quenched by the addition of saturated aqueous NH4Cl (5 mL) and extracted with toluene(3 × 5 mL). The combined organic layers were dried over anhydrous Na2SO4, and evaporated under reduced pressure. Purification of the residue by column chromatography (EtOAc in hexane)afforded the corresponding alcohol. The ee was determined by GC or HPLC analyses using achiral column. General method for the GC analysis: Supelco-DEXTM 120, TInj: 250 °C, TDet:250 °C (FID), N2: 1 mL/min, split: 100:1, oven: 60 °C η 140 °C (10 °C/min). Stage 1: With (Sa)-1-[2-diphenylhydroxymethyl-6-(trifluoromethyl)phenyl]-2-(1-pyrrolidinomethyl)-1H-pyrrole in hexane, Time= 1h, T= 20 °C , Inert atmosphere Stage 2: in hexane, Time= 4h, T= 20 °C , Inert atmosphere, Temperature, Overall yield = 92 percent; enantioselective reaction Faigl, Ferenc; Erdlyi, Zsuzsa; Dek, Szilvia; Nyerges, Mikls; Mtravölgyi, Bla; Tetrahedron Letters; vol. 55; nb. 50; (2014); p. 6891 - 6894 View in Reaxys General procedure for the addition of diethylzinc to aldehydes General procedure: The chiral η-hydroxy-2-oxazoline (0.05 mmol) was dissolved in the desired solvent (1 mL) then a solution ofdiethylzinc was added (2.5 mL, 2.5 mmol, 1 mol L−1 inhexane) at 25 °C. The mixture was stirred for 20 min andthen cooled to 0 °C. A solution of the aldehyde (2 mmol in 3 mL of solvent) was added dropwise. After 2 h, the cooling bath was removed and the reaction was quenched with an aqueous saturated solution of NH4Cl (5 mL),extracted with a mixture of hexane (2 mL) and diethyl ether (2 mL). The organic layer was dried over anhydrous Na2SO4, and after filtration, the solvent was eliminated under reduced pressure. The product was purified by flash chromatography using hexane/ethyl acetate 9:1 as eluent leading to the corresponding secondary alcohol.The enantiomeric excess was determined by chiral gas chromatography. Stage 1: With (1R,2S,5R)-1-((4,4-dimethyl-4,5-dihydrooxazol-2-yl)methyl)-2-isopropyl-5-methylcyclohexanol in hexane, Time= 0.333333h, T= 20 °C Stage 2:, Time= 2h, T= 0 °C , Overall yield = 94 percent; enantioselective reaction Marques, Francisco A.; Wosch, Celso L.; Frensch, Gustavo; Labes, Ricardo; Maia, Beatriz H. L. N. S.; Salom, Kahlil S.; Barisona, Andersson; Guerrero, Palimcio G.; Journal of the Brazilian Chemical Society; vol. 26; nb. 1; (2015); p. 165 - 170 View in Reaxys Asymmetric addition of diethylzinc to aldehydes: general procedure General procedure: The chiral catalyst (0.1mmol) in dry toluene (5mL) was placed in a round-bottom flask. The mixture was cooled to 0°C and a solution of diethylzinc (1.0M in hexane, 3.0mmol) was added under argon. After stirring for 30min, an aldehyde (1.0mmol) was added at 0°C, and the mixture was stirred at room temperature overnight. Next, 5percent HCl aqueous solution was added, the layers were separated and the aqueous phase was extracted with diethyl ether (4×10mL). The combined organic layers were washed with brine (10mL) and dried over anhydrous MgSO4. The solvents were evaporated to afford crude alcohols 14, which were purified via column chromatography on silica gel (hexane with ethyl acetate in gradient). The yields, specific rotations, enantiomeric excess values and the absolute configurations of products 14 are shown in Table 4. The spectroscopic data were in full agreement with those reported in the literature.13 Stage 1: With 2-(1-hydroxyethyl)-1-tritylaziridine in hexane, toluene, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, T= 0 - 20 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 91 percent; enantioselective reaction Jarzyski, Szymon; Lesniak, Stanislaw; Pieczonka, Adam M.; Rachwalski, Michal; Tetrahedron Asymmetry; vol. 26; nb. 1; (2015); p. 35 - 40 View in Reaxys Stage 1: With (Ra)-1-[2-(N,N-dimethylamino)methyl-6-(trifluoromethyl)phenyl]-1H-pyrrole-2-diphenylmethanol in hexane, Time= 1h, T= 24 °C , Inert atmosphere Stage 2: in hexane, Time= 4h, T= 24 °C , Inert atmosphere, Reagent/catalyst, Temperature, Overall yield = 94 percent; enantioselective reaction Faigl; Deák; Erdélyi; Holczbauer; Czugler; Nyerges; Mátravölgyi; Chirality; vol. 27; nb. 3; (2015); p. 216 - 222 View in Reaxys With 2-[(1S)-1-hydroxyethyl]-3-{(3R)-3-[(1R)-1-hydroxyethyl]-2,2-dimethylaziridin-1-yl}quinazolin-4(3H)-one in hexane, toluene, Time= 20h, T= 0 °C , Inert atmosphere, Solvent, enantioselective reaction Celik, Saffet; Cakici, Murat; Kilic, Hamdullah; Sahin, Ertan; Tetrahedron Asymmetry; vol. 26; nb. 2-3; (2015); p. 152 - 157 View in Reaxys

104/258

2018-07-03 17:29:03

4.11. Typical procedure for the addition of diethylzinc to aldehyde General procedure: To a solution of 4 (0.05 mmol) in freshly distilled diethyl ether(1 mL) diethylzinc (1 mL of 1 M hexane solution, 1 mmol) was added at ambient temperature under argon. The mixture was stirredfor 1 h and then cooled to 15 C. A solution of aldehyde (0.5 mmol) in diethyl ether (1 mL) was added via syringe and the mixture was stirred for 48 h. The reaction was then quenched bythe addition of saturated NH4Cl solution (4 mL), and diphenylmethane (0.25 mmol) was added as an internal standard. The mixture was extracted with EtOAc (3 10 mL) and the combined organic extracts were washed with water (10 mL) and brine (10 mL). The organic layer was dried over anhydrous Na2SO4 and concentrated in vacuo. Conversion and yield were determined from the crude mixture by 1H NMR analysis. The crude product was purified by preparative thin layer chromatography on silica gel (hexane/EtOAc,90:10) and the enantiomeric excess of the addition product was determined by GC on a Chiral b-DEX 120 capillary column.11b With 2-[(1S)-1-hydroxyethyl]-3-{(3S)-3-[(1R)-1-hydroxyethyl]-2,2-dimethylaziridin-1-yl}quinazolin-4(3H)-one in hexane, toluene, Time= 48h, T= -30 °C , Inert atmosphere, Reagent/catalyst, Temperature, Time, enantioselective reaction Celik, Saffet; Cakici, Murat; Kilic, Hamdullah; Sahin, Ertan; Tetrahedron Asymmetry; vol. 26; nb. 2-3; (2015); p. 152 - 157 View in Reaxys Stage 1: With (R,R)-(+)-1,2-bis(2-phenylphenyl)ethane-1,2-diol in hexane, dichloromethane, Time= 0.333333h, T= 20 °C , Inert atmosphere Stage 2: in hexane, dichloromethane, Time= 24h, T= 0 °C , Inert atmosphere, Reagent/catalyst, Solvent, Overall yield = 32 percent; enantioselective reaction Gök, Yaar; Külolu, Soner; Gök, Halil Zeki; Kekec, Levent; Applied Organometallic Chemistry; vol. 28; nb. 11; (2014); p. 835 - 838 View in Reaxys With (R,R)-(+)-1,2-bis(2-phenylphenyl)ethane-1,2-diol in hexane, dichloromethane, Time= 24h, T= 20 °C , Reagent/catalyst, Solvent, Overall yield = 32 percent; Optical yield = 79 percent ee; enantioselective reaction Gök, Yaşar; Küloglu, Soner; Gök, Halil Zeki; Kekecş, Levent; Journal of Pharmacy and Pharmacology; vol. 28; nb. 11; (2014); p. 835 - 838 View in Reaxys With chiral copolymer (copoly(1/2)) in tetrahydrofuran, Time= 24h, T= 0 °C , Schlenk technique, Inert atmosphere, Reagent/ catalyst, Overall yield = 19.3 percent; enantioselective reaction Liu, Lijia; Long, Qing; Aoki, Toshiki; Zhang, Geng; Kaneko, Takashi; Teraguchi, Masahiro; Zhang, Chunhong; Wang, Yudan; Chirality; vol. 27; nb. 8; (2015); p. 454 - 458 View in Reaxys With chiral copolymer (copoly(1/2)) in tetrahydrofuran, Time= 24h, T= 0 °C , Schlenk technique, Inert atmosphere, Reagent/ catalyst, Overall yield = 20 percent; enantioselective reaction Liu, Lijia; Long, Qing; Aoki, Toshiki; Zhang, Geng; Kaneko, Takashi; Teraguchi, Masahiro; Zhang, Chunhong; Wang, Yudan; Chirality; vol. 27; nb. 8; (2015); p. 454 - 458 View in Reaxys 4.5 Asymmetric ethylation of arylaldehyde with diethylzinc General procedure: Diethylzinc (1.1ml, 1M solution in hexane) was added to a stirred solution of ligand (0.033mmol) in toluene (1.0ml) under Ar at room temperature. After stirring the resulting reaction mixture at this temperature for 15min, benzaldehyde (0.05ml, 0.55mmol) was added. Stirring was continued for 24h at room temperature. At the end of this period, the reaction mixture was diluted with ethyl acetate (10ml), quenched with a saturated aqueous solution of NH4Cl (10ml), and the two layers were separated. The aqueous layer was extracted with ethyl acetate (2×10ml). The combined organic layers were dried over Na2SO4, concentrated and purified by flash column chromatography on silica gel using hexane–ethyl acetate. 1-Phenyl-1-propanol was obtained in 81percent yield (61mg, 0.446 mmol). Chiral HPLC was used to determine the ee. Other asymmetric reaction using various aldehydes and ligands were examined with the same procedure. With C36H30N2O6 in hexane, toluene, Time= 24h, T= 20 °C , Inert atmosphere, Overall yield = 81 percent; Overall yield = 61 mg; enantioselective reaction Ueda, Yuki; Yagishita, Fumitoshi; Ishikawa, Hiroki; Kaji, Yuki; Baba, Nozomi; Kasashima, Yoshio; Mino, Takashi; Sakamoto, Masami; Tetrahedron; vol. 71; nb. 36; (2015); p. 6254 - 6258; Art.No: 26920 View in Reaxys

105/258

2018-07-03 17:29:03

4.5 Asymmetric ethylation of arylaldehyde with diethylzinc General procedure: Diethylzinc (1.1ml, 1M solution in hexane) was added to a stirred solution of ligand (0.033mmol) in toluene (1.0ml) under Ar at room temperature. After stirring the resulting reaction mixture at this temperature for 15min, benzaldehyde (0.05ml, 0.55mmol) was added. Stirring was continued for 24h at room temperature. At the end of this period, the reaction mixture was diluted with ethyl acetate (10ml), quenched with a saturated aqueous solution of NH4Cl (10ml), and the two layers were separated. The aqueous layer was extracted with ethyl acetate (2×10ml). The combined organic layers were dried over Na2SO4, concentrated and purified by flash column chromatography on silica gel using hexane–ethyl acetate. 1-Phenyl-1-propanol was obtained in 81percent yield (61mg, 0.446 mmol). Chiral HPLC was used to determine the ee. Other asymmetric reaction using various aldehydes and ligands were examined with the same procedure. With C36H34N2O6 in hexane, toluene, Time= 24h, T= 20 °C , Inert atmosphere, Catalytic behavior, Reagent/catalyst, Temperature, Overall yield = 77 percent; enantioselective reaction Ueda, Yuki; Yagishita, Fumitoshi; Ishikawa, Hiroki; Kaji, Yuki; Baba, Nozomi; Kasashima, Yoshio; Mino, Takashi; Sakamoto, Masami; Tetrahedron; vol. 71; nb. 36; (2015); p. 6254 - 6258; Art.No: 26920 View in Reaxys General procedure for the addition of ZnEt2 to benzaldehyde General procedure: The corresponding amount of 1,2-aminoalcohol was suspended in dry toluene (0,5 mL) under argonatmosphere, at 0 °C and a 1.1 M solution of ZnEt2 in hexane (2 mmol) was added. The mixture was stirredat this temperature for 30 min and then, benzaldehyde (1 mmol) was added dropwise. Stirring wascontinued at 0 °C for 30 min and then at room temperature for 24 h. The reaction was quenched at 0 °C byaddition of water. The crude was diluted with ethyl acetate and filtered through a silica column using asintered glass funnel. The solvent was evaporated under reduced pressure and purified by flashchromatography, allowing the separation of 1-phenyl-1-propanol from the 1,2-aminoalcohol, which couldbe recover quantitatively and reused. The enantiomeric excess was determined by the use of HPLC(Chiralcel OD) using a mixture hexane - isopropanol (97:3) as the eluent (1 mL / min): (R)-1-phenyl-1-propanol, 9 min; (S)-1-phenyl-1-propanol, 11 min. Stage 1: With C25H27NO3 in hexane, toluene, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, Time= 24.5h, T= 0 - 20 °C , Inert atmosphere, Overall yield = 96 percent; enantioselective reaction Zanardi, María M.; Suárez, Alejandra G.; Tetrahedron Letters; vol. 56; nb. 24; (2015); p. 3762 - 3765 View in Reaxys General procedure for the addition of ZnEt2 to benzaldehyde General procedure: The corresponding amount of 1,2-aminoalcohol was suspended in dry toluene (0,5 mL) under argonatmosphere, at 0 °C and a 1.1 M solution of ZnEt2 in hexane (2 mmol) was added. The mixture was stirredat this temperature for 30 min and then, benzaldehyde (1 mmol) was added dropwise. Stirring wascontinued at 0 °C for 30 min and then at room temperature for 24 h. The reaction was quenched at 0 °C byaddition of water. The crude was diluted with ethyl acetate and filtered through a silica column using asintered glass funnel. The solvent was evaporated under reduced pressure and purified by flashchromatography, allowing the separation of 1-phenyl-1-propanol from the 1,2-aminoalcohol, which couldbe recover quantitatively and reused. The enantiomeric excess was determined by the use of HPLC(Chiralcel OD) using a mixture hexane - isopropanol (97:3) as the eluent (1 mL / min): (R)-1-phenyl-1-propanol, 9 min; (S)-1-phenyl-1-propanol, 11 min. Stage 1: With C20H19NO3 in hexane, toluene, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, Time= 48.5h, T= 0 - 20 °C , Inert atmosphere, Catalytic behavior, Reagent/catalyst, Overall yield = 80 percent; enantioselective reaction Zanardi, María M.; Suárez, Alejandra G.; Tetrahedron Letters; vol. 56; nb. 24; (2015); p. 3762 - 3765 View in Reaxys 4.2. General procedure for the enantioselective diethylzincaddition to arylaldehydes General procedure: To a stirring mixture of ligand 1h (0.005 mmol, 1 mol percent) intoluene (5 mL), diethylzinc (1 M in nhexane, 1.5 mL) was addedunder a nitrogen atmosphere. The mixture was cooled to 0 C,and stirred for 0.5 h, followed by the addition of the correspondingfreshly distilled aldehyde (0.5 mmol). The mixture was stirred for48 h at the same temperature, and then quenched with saturatedaqueous NH4Cl (4 mL). The organic layer was separated and theaqueous phase was extracted with Et2O (10 mL 3). The organiclayers were combined and dried over anhydrous MgSO4 and evaporatedunder reduced pressure. The residue was purified by thepreparative silica gel TLC plate (ethylacetate and petroleum ether,1:6, v/v) to afford the corresponding chiral alcohol as a colorless oilor light-yellow solid. The enantiomeric excess was determined byHPLC analysis using a Chiralcel OD-H or OB-H column. Conditionsof HPLC analysis: Chiralcel OD-H and Chiralcel OB-H4.6 mm 250 mm; detection, 254 nm light. The absolute configurationsof the products were assigned by comparison to the literaturedata. In all cases, the product chromatograms were comparedagainst a known racemic mixture.

106/258

2018-07-03 17:29:03

Stage 1: With (2S)-1-piperonylmethylaziridin-2-yl(dibenzyl)methanol in hexane, toluene, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, Time= 48h, T= 0 °C , Inert atmosphere, Temperature, Reagent/catalyst, Overall yield = 81 percent; enantioselective reaction Wang, Xiaojuan; Zhao, Wenxian; Li, Gaowei; Liu, Guanjun; Wang, Jin; Wang, Mincan; Liu, Lantao; Tetrahedron Asymmetry; vol. 26; nb. 15-16; (2015); p. 815 - 820; Art.No: 59322 View in Reaxys 4.6. General procedure for enantioselective alkylation reactions General procedure: To the chiral ligand (0.15 mmol) and benzaldehyde (1 mmol) inan inert atmosphere, 4 mL of solvent was added. The temperature of the reaction mixture was lowered to 0 °C and diethylzinc (2 mmol, as a 1 M hexane solution) was added. The reaction was stirred for 10 min at 0 C and then for 24 h at 0 °C or room temperature. After this time a saturated ammonium chloride solution(1 mL) followed by 2 M HCl (1 mL) was added and the reaction mixture was extracted with diethyl ether. The organic phases were washed with water and brine and dried over anhydrous sodium sulfate. The resulting solution was analyzed by GC on a chiralc-cyclodextrin capillary column in order to determine the ee ofthe products.17 With C18H28N2O in hexane, cyclohexane, Time= 24h, T= 0 - 20 °C , Inert atmosphere, Schlenk technique, Reagent/catalyst, Temperature, enantioselective reaction Murtinho, Dina; Ogihara, Camila H.; Serra, M. Elisa Silva; Tetrahedron Asymmetry; vol. 26; nb. 21-22; (2015); p. 1256 1260 View in Reaxys 4.6. General procedure for enantioselective alkylation reactions General procedure: To the chiral ligand (0.15 mmol) and benzaldehyde (1 mmol) inan inert atmosphere, 4 mL of solvent was added. The temperature of the reaction mixture was lowered to 0 °C and diethylzinc (2 mmol, as a 1 M hexane solution) was added. The reaction was stirred for 10 min at 0 C and then for 24 h at 0 °C or room temperature. After this time a saturated ammonium chloride solution(1 mL) followed by 2 M HCl (1 mL) was added and the reaction mixture was extracted with diethyl ether. The organic phases were washed with water and brine and dried over anhydrous sodium sulfate. The resulting solution was analyzed by GC on a chiralc-cyclodextrin capillary column in order to determine the ee ofthe products.17 With (1R,3S)-N1,N1-dimethyl-N3-salicylidene-1,2,2-trimethylcyclopentane-1,3-diamine in hexane, cyclohexane, Time= 24h, T= 0 °C , Inert atmosphere, Schlenk technique, Catalytic behavior, Reagent/catalyst, Temperature, Solvent, enantioselective reaction Murtinho, Dina; Ogihara, Camila H.; Serra, M. Elisa Silva; Tetrahedron Asymmetry; vol. 26; nb. 21-22; (2015); p. 1256 1260 View in Reaxys 4.6. Addition of diethylzinc on aryldehydes General procedure: 4.6.1. General procedure. In an oven-dried 5 mL flask under argon atmosphere, the ligand (0.1 equiv, 0.1 mmol) was dissolved in 2.5 mL of anhydrous toluene and diethylzinc (1.5 M in toluene, 2 mmol) was added dropwise. The solution was cooled to 0 °C for 15 min and the aldehyde (1 equiv, 1 mmol) was added as a single portion. The mixture was then warmed to room temperature and stirred for 48 h before 1 N HCl was added. The resulting alcohol was extracted with three portions of EtOAc. The organic layers were then combined, washed with brine, dried with Na2SO4, and concentrated in vacuo, giving an oil from which conversion and enantiomeric excess were determined by GC. In one case involving benzaldehyde and ligand 23a (Table 3, entry 1), the crude product was purified by flash chromatography (5:95 EtOAc/hexanes), giving 81percent isolated yield of 32. Commercially available (S)-1-phenyl-1-propanol was used for enantiomer identification on the GC chromatograms. Products 33 and 35, as control experiments, were also prepared from Grignard addition reactions and analyzed by GC. Stage 1: With (2R,5R)-2,5-dibenzyl-1,4-dimethylpiperazine in toluene, Time= 0.25h, T= 0 °C , Inert atmosphere Stage 2: in toluene, Time= 48h, T= 0 - 20 °C , Inert atmosphere, enantioselective reaction Bérubé, Christopher; Cardinal, Sébastien; Boudreault, Pierre-Luc; Barbeau, Xavier; Delcey, Nicolas; Giguère, Martin; Gleeton, Dave; Voyer, Normand; Tetrahedron; vol. 71; nb. 42; (2015); p. 8077 - 8084 View in Reaxys S.8 Typical procedure forthe addition of diethylzinc to aldehydes General procedure: To a solution of the chiralligand 4-7 (5 molpercent) a solution (1mol/L) of diethylzinc in hexanes (1.25 mmol) was added and thesolution was stirred at room temperature for 20 min. The system was cooled to 0oC and a solution of the respective aldehyde (1.0 mmol) in hexane (1mL/mmol) was added. The resulting solution was stirred for 2 h. The temperaturewas elevated to 24 oC and saturated NH4Cl (2 mL) wasadded. The product was extracted using a mixture (1:1, v/v) of ethyl ether andhexane (3 x 2 mL) and the organic layer was dried over Na2SO4,filtered and the resulting solution was analyzed by

107/258

2018-07-03 17:29:03

chiral gas chromatography.The crude product was purified by flash chromatography using a mixture ofhexane/ethyl acetate (9:1, v/v). Stage 1: With (1R,2R,3S,5R)-2,6,6-trimethyl-3-(piperidin-1-yl)bicyclo[3.1.1]heptan-2-ol in hexane, Time= 0.333333h, T= 20 °C Stage 2: in hexane, Time= 2h, T= 0 °C , Overall yield = 94 percent; enantioselective reaction Frensch, Gustavo; Labes, Ricardo; Wosch, Celso Luiz; Munaretto, Laieli Dos Santos; Salomé, Kahlil Schwanka; Guerrero, Palimécio G.; Marques, Francisco A.; Tetrahedron Letters; vol. 57; nb. 3; (2016); p. 420 - 422 View in Reaxys S.8 Typical procedure forthe addition of diethylzinc to aldehydes General procedure: To a solution of the chiralligand 4-7 (5 molpercent) a solution (1mol/L) of diethylzinc in hexanes (1.25 mmol) was added and thesolution was stirred at room temperature for 20 min. The system was cooled to 0oC and a solution of the respective aldehyde (1.0 mmol) in hexane (1mL/mmol) was added. The resulting solution was stirred for 2 h. The temperaturewas elevated to 24 oC and saturated NH4Cl (2 mL) wasadded. The product was extracted using a mixture (1:1, v/v) of ethyl ether andhexane (3 x 2 mL) and the organic layer was dried over Na2SO4,filtered and the resulting solution was analyzed by chiral gas chromatography.The crude product was purified by flash chromatography using a mixture ofhexane/ethyl acetate (9:1, v/v). Stage 1: With (1S,2S,3R,5S)-2,6,6-trimethyl-3-(piperidin-1-yl)bicyclo[3.1.1]heptan-2-ol in hexane, Time= 0.333333h, T= 20 °C Stage 2: in hexane, Time= 2h, T= 0 °C , Overall yield = 95 percent; enantioselective reaction Frensch, Gustavo; Labes, Ricardo; Wosch, Celso Luiz; Munaretto, Laieli Dos Santos; Salomé, Kahlil Schwanka; Guerrero, Palimécio G.; Marques, Francisco A.; Tetrahedron Letters; vol. 57; nb. 3; (2016); p. 420 - 422 View in Reaxys Stage 1: With (1R,2S,3R,4S)-3-[(3-tert-butyl-2-hydroxybenzyl)amino]-2-hydroxy-1,7,7-trimethylbicyclo[2.2.1]heptane in toluene, T= 0 °C Stage 2: in toluene, Time= 6h, T= 0 °C , Catalytic behavior, Reagent/catalyst, Solvent, Temperature, Overall yield = 90 percent; enantioselective reaction Lee, Dong-Sheng; Chang, Shu-Ming; Ho, Chun-Ying; Lu, Ta-Jung; Chirality; vol. 28; nb. 1; (2016); p. 65 - 71 View in Reaxys With (RP)-1-(bezofuran-2-yl)-2-dimethylaminomethyl-3-(hydroxydiphenylmethyl)ferrocene in toluene, T= 0 °C , Overall yield = 90 percent; Overall yield = 134.8 mg; enantioselective reaction Gao, De-Wei; Gu, Qing; You, Shu-Li; Journal of the American Chemical Society; vol. 138; nb. 8; (2016); p. 2544 - 2547 View in Reaxys With (+)-(1S,2R)-2-[(R)-phenylsulfinyl]-2,3-dihydro-1H-inden-1-ol in hexane, toluene, Inert atmosphere, Reagent/catalyst Boyd, Derek R.; Sharma, Narain D.; Malone, John F.; Ljubez, Vera; Murphy, Deirdre; Shepherd, Steven D.; Allen, Christopher C. R.; Organic and Biomolecular Chemistry; vol. 14; nb. 9; (2016); p. 2651 - 2664 View in Reaxys With (+)-(1S,3S)-2-[(R)-phenylsulfinyl]-2,3-dihydro-1H-inden-1-ol in hexane, toluene, Inert atmosphere, Reagent/catalyst Boyd, Derek R.; Sharma, Narain D.; Malone, John F.; Ljubez, Vera; Murphy, Deirdre; Shepherd, Steven D.; Allen, Christopher C. R.; Organic and Biomolecular Chemistry; vol. 14; nb. 9; (2016); p. 2651 - 2664 View in Reaxys With diphenyl(2-((3R,7aS)-2-phenylhexahydro-1H-pyrrolo[1,2-c]imidazol-3-yl)phenyl)methanol in hexane, cyclohexane, Time= 7h, T= 0 - 20 °C , Inert atmosphere, Overall yield = 86 percent; enantioselective reaction Asami, Masatoshi; Hasome, Ayano; Yachi, Naoyuki; Hosoda, Naoya; Yamaguchi, Yoshitaka; Ito, Suguru; Tetrahedron Asymmetry; vol. 27; nb. 7-8; (2016); p. 322 - 329 View in Reaxys General procedure for the addition of ZnEt2 to aromatic aldehydes. General procedure: The corresponding amount of Wang resin-supported aminoalcohol 8a-d was suspended in a minimum amount of dry toluene to swell the resin under argon atmosphere at 0 C and a 1.1 M solution of ZnEt2 in toluene (2 mmol) was added. The mixture was stirred at 0 C for 30 min. After reaching room temperature, the corresponding aldehyde (1 mmol) was

108/258

2018-07-03 17:29:03

added and stirring was continued until total consumption of the starting material. After filtration in a polypropylene cartridge to recover the supported catalyst, the liquid residue was diluted with ethyl acetate and filtered through a silica or celite column using a sintered glass funnel. The solvent was evaporated under reduced pressure to give an oily residue. The 1H NMR (CDCl3) of this residue allows to obtain the yield of the reaction using the following signals when the starting material was benzaldehyde (η): benzaldehyde (9.90, s, 1 H); 1-phenyl-1-propanol (4.48, S-9t, 1 H); benzyl alcohol (4.58, s, 2 H). The enantiomeric excesses were determined by GC or HPLC analyses. Conditions of GC analyses: η-DEX or η-DEX column, 30 m length, 0.25 mm inner diameter, He as carrier gas (1.0 mL/min). 115 °C. tR R isomer 55.0 min, tR S isomer 55.6 min. For 1-(4-methoxyphenyl)-1propanol: 115 °C. tR R isomer 77.6 min, tR S isomer 78.2 min. For 1-(4-chlorophenyl)-1-propanol: 115 °C. tR R isomer 75.4 min, tR S isomer 76.1 min. Conditions of HPLC anlyses: ChiralcelOD column (Hexane / isopropanol 97 / 3, 1 mL / min, 254 nm): (R)-1-phenyl-1-propanol, 9.0 min; (S)-1-phenyl-1-propanol, 11.0 min. The resin was sequentially washed with THF / Acetic Acid 90 / 10 (3 x 4mL), H2O (3 x 4 mL), THF (3 x 4 mL) and DCM (3 x 4 mL) and could be recover quantitatively. Stage 1: With Wang resin-supported aminoalcohol in toluene, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in toluene, Time= 48h, T= 25 °C , Inert atmosphere, Reagent/catalyst, Concentration, Overall yield = 90 percentSpectr.; enantioselective reaction Botta, María C.; Biava, Hernán D.; Spanevello, Rolando A.; Mata, Ernesto G.; Suárez, Alejandra G.; Tetrahedron Letters; vol. 57; nb. 20; (2016); p. 2186 - 2189 View in Reaxys Stage 1: With (1R,2R,3R,6S)-3-aminomethyl-7,7-dimethylbicyclo[4.1.0]heptane-2,3-diol hydrochloride in hexane, Time= 0.416667h, T= 20 °C , Inert atmosphere Stage 2: in hexane, T= 20 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 89 percent; enantioselective reaction Szakonyi, Zsolt; Csör, Árpád; Csámpai, Antal; Fülöp, Ferenc; Chemistry - A European Journal; vol. 22; nb. 21; (2016); p. 7163 - 7173 View in Reaxys Stage 1: With (4aR,6aS,7aR,7bR)-7,7-dimethyl-4a-hydroxy-3-((S)-1-phenylethyl)decahydrocyclopropa[3,4]benzo[1,2-e] [1,3]oxazine in hexane, Time= 0.416667h, T= 20 °C , Inert atmosphere Stage 2: in hexane, T= 20 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 87 percent; enantioselective reaction Szakonyi, Zsolt; Csör, Árpád; Csámpai, Antal; Fülöp, Ferenc; Chemistry - A European Journal; vol. 22; nb. 21; (2016); p. 7163 - 7173 View in Reaxys With 1-((dimethylamino)methyl)-7,7-dimethylbicyclo[2.2.1]heptan-2-ol in hexane, Time= 48h, T= 0 °C , Catalytic behavior, Reagent/catalyst, Solvent, Overall yield = 93 percent; enantioselective reaction Wu, Hsyueh-Liang; Wu, Ping-Yu; Cheng, Ying-Ni; Uang, Biing-Jiun; Tetrahedron; vol. 72; nb. 21; (2016); p. 2656 - 2665 View in Reaxys With (5S,6S,8R)-3-benzyl-4,4,8-trimethyl-1-oxa-3-azaspiro[4.5]decan-6-ol in hexane, T= 20 °C , Reagent/catalyst, Overall yield = 87 percent; enantioselective reaction Gonda, Tímea; Szakonyi, Zsolt; Csámpai, Antal; Haukka, Matti; Fülöp, Ferenc; Tetrahedron Asymmetry; vol. 27; nb. 11-12; (2016); p. 480 - 486 View in Reaxys With (4aR,7R,8aR)-3-benzyl-4,4,7-trimethylhexahydrobenzo[e][1,3]oxazin-4a-ol in hexane, T= 20 °C , Reagent/catalyst, Overall yield = 88 percent; enantioselective reaction Gonda, Tímea; Szakonyi, Zsolt; Csámpai, Antal; Haukka, Matti; Fülöp, Ferenc; Tetrahedron Asymmetry; vol. 27; nb. 11-12; (2016); p. 480 - 486 View in Reaxys Stage 1: With titanium(IV) isopropylate, (1R,2R)-1,2-bis(3η-bromophenyl)-ethane-1,2-diol in hexane, dichloromethane, Time= 0.333333h, T= 20 °C , Inert atmosphere Stage 2: in hexane, dichloromethane, Time= 24h, T= 20 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 42 percent; enantioselective reaction Gök, Yaşar; Kiliçarslan, Seda; Gök, Halil Zeki; Karayiğit, İlker Ümit; Chirality; (2016); p. 593 - 598 View in Reaxys

109/258

2018-07-03 17:29:03

Stage 1: With (1R,2R)-1,2-bis([1,1’-biphenyl]-4-yl)-ethane-1,2-diol in hexane, toluene, Time= 0.333333h, T= 20 °C , Inert atmosphere Stage 2: in hexane, toluene, Time= 24h, T= 20 °C , Inert atmosphere, Reagent/catalyst, Solvent, Overall yield = 14 percent; enantioselective reaction Gök, Yaşar; Kiliçarslan, Seda; Gök, Halil Zeki; Karayiğit, İlker Ümit; Chirality; (2016); p. 593 - 598 View in Reaxys 4.22. Enantioselective addition of diethylzinc to benzaldehyde in presence of ligands 15-19, 29-35, 45 and 46 (General procedure) Enantioselective addition of diethylzinc to benzaldehyde in presence of ligands 15-19, 29-35, 45 and 46 (General procedure) To a solution of the corresponding ligand in 6 ml of hexane or toluene, Et2Zn (5.6 ml, 5.60 mmol of 1 M solution in hexane) was added dropwise at 0 °C. The mixture was stirred for 30 min at 0 °C and then benzaldehyde (0.288 ml, 2.83 mmol) was added at 0 °C. The reaction was stirred at room temperature and monitored by TLC (petroleum ether/Et2O = 5:1) until the full consumption of benzaldehyde. The mixture was quenched at 0 °C (aq. NH4Cl), extracted with Et2O (3 * 20 ml) and organic phase was dried over anhydrous Na2SO4. The solvent was evaporated in vacuo and the crude product was chromatographed (15 g silica gel, petroleum ether/Et2O = 6:1) to obtain pure 1-phenyl-1-propanol as a mixture of both enantiomers. For the ee determination of 1-phenyl-1-propanol, see Section 4.1 . Stage 1: With (1R,2R,4S,E)-3-(ferrocenylmethylidene)-2-(2-((dimethylamino)methyl)phenyl)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol in hexane, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, T= 0 - 20 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 99 percent; enantioselective reaction Kamenova-Nacheva, Mariana; Dobrikov, Georgi M.; Dimitrov, Vladimir; Tetrahedron Asymmetry; vol. 27; nb. 17-18; (2016); p. 852 - 864 View in Reaxys 4.22. Enantioselective addition of diethylzinc to benzaldehyde in presence of ligands 15-19, 29-35, 45 and 46 (General procedure) Enantioselective addition of diethylzinc to benzaldehyde in presence of ligands 15-19, 29-35, 45 and 46 (General procedure) To a solution of the corresponding ligand in 6 ml of hexane or toluene, Et2Zn (5.6 ml, 5.60 mmol of 1 M solution in hexane) was added dropwise at 0 °C. The mixture was stirred for 30 min at 0 °C and then benzaldehyde (0.288 ml, 2.83 mmol) was added at 0 °C. The reaction was stirred at room temperature and monitored by TLC (petroleum ether/Et2O = 5:1) until the full consumption of benzaldehyde. The mixture was quenched at 0 °C (aq. NH4Cl), extracted with Et2O (3 * 20 ml) and organic phase was dried over anhydrous Na2SO4. The solvent was evaporated in vacuo and the crude product was chromatographed (15 g silica gel, petroleum ether/Et2O = 6:1) to obtain pure 1-phenyl-1-propanol as a mixture of both enantiomers. For the ee determination of 1-phenyl-1-propanol, see Section 4.1 . Stage 1: With C27H33FeNO4S in hexane, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in hexane, T= 0 - 20 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 59 percent; enantioselective reaction Kamenova-Nacheva, Mariana; Dobrikov, Georgi M.; Dimitrov, Vladimir; Tetrahedron Asymmetry; vol. 27; nb. 17-18; (2016); p. 852 - 864 View in Reaxys 4.6. General procedure for enantioselective alkylations General procedure: To the chiral ligand (0.15 mmol) and aldehyde (1 mmol) in an inert atmosphere, 4 mL of dry cyclohexane were added. The temperature of the reaction mixture was lowered to 0°C and diethylzinc (2 mmol, 2 mL, as a 1 M hexane solution) was added. The reaction was stirred 10 min at 0°C and then for 24 h at the required temperature. Subsequently, a saturated ammonium chloride solution (1 mL) was added, followed by 2 M HCl (1 mL) and the reaction mixture was extracted with diethyl ether. The joint organic phases were washed with water and brine and dried over anhydrous sodium sulfate. The resulting solution was analyzed by GC on a chiral η-cyclodextrin capillary column in order to determine the ee of the products.24

110/258

2018-07-03 17:29:03

With (S)-methyl 2-(2-methoxyphenyl)-5,5-dimethyl-1,3-thiazolidine-4-carboxylate in hexane, cyclohexane, Time= 24.1667h, T= 0 - 20 °C , Inert atmosphere, Schlenk technique, Reagent/catalyst, Overall yield = 99 percentChromat.; enantioselective reaction Serra, M. Elisa Silva; Costa, Dora; Murtinho, Dina; Tavares, Nélia C.T.; Pinho e Melo, Teresa M.V.D.; Tetrahedron; vol. 72; nb. 39; (2016); p. 5923 - 5927 View in Reaxys 4.6. General procedure for enantioselective alkylations General procedure: To the chiral ligand (0.15 mmol) and aldehyde (1 mmol) in an inert atmosphere, 4 mL of dry cyclohexane were added. The temperature of the reaction mixture was lowered to 0°C and diethylzinc (2 mmol, 2 mL, as a 1 M hexane solution) was added. The reaction was stirred 10 min at 0°C and then for 24 h at the required temperature. Subsequently, a saturated ammonium chloride solution (1 mL) was added, followed by 2 M HCl (1 mL) and the reaction mixture was extracted with diethyl ether. The joint organic phases were washed with water and brine and dried over anhydrous sodium sulfate. The resulting solution was analyzed by GC on a chiral η-cyclodextrin capillary column in order to determine the ee of the products.24 With (R)-methyl 2,2-diethylthiazolidine-4-carboxylate in hexane, cyclohexane, Time= 24.1667h, T= 0 - 20 °C , Inert atmosphere, Schlenk technique, Reagent/catalyst, Overall yield = 99 percentChromat.; enantioselective reaction Serra, M. Elisa Silva; Costa, Dora; Murtinho, Dina; Tavares, Nélia C.T.; Pinho e Melo, Teresa M.V.D.; Tetrahedron; vol. 72; nb. 39; (2016); p. 5923 - 5927 View in Reaxys With Ti modified chiral porous covalent organic framework (R,R)-CCOF-2 in hexane, toluene, Time= 10h, T= -30 °C , Inert atmosphere, enantioselective reaction Wang, Xiuren; Han, Xing; Zhang, Jie; Wu, Xiaowei; Liu, Yan; Cui, Yong; Journal of the American Chemical Society; vol. 138; nb. 38; (2016); p. 12332 - 12335 View in Reaxys With Ti modified chiral porous covalent organic framework (S,S)-CCOF-2 in hexane, toluene, Time= 10h, T= -30 °C , Inert atmosphere, enantioselective reaction Wang, Xiuren; Han, Xing; Zhang, Jie; Wu, Xiaowei; Liu, Yan; Cui, Yong; Journal of the American Chemical Society; vol. 138; nb. 38; (2016); p. 12332 - 12335 View in Reaxys 4 : Example 4. Asymmetric addition of diethylzinc and acid Under an argon atmosphere, in a dry three-necked flask substituted benzaldehyde 3 (1.1mmol, 1equiv.) And catalyst (Rp) -II-1 (29.8mg, 0.055mmol, 5molpercent), toluene (1.5mL).At 0 , diethyl zinc (4.4mmol, 4.0equiv.). At this temperature, while the reaction to benzaldehyde disappeared (the reaction mixture was quenched using 1 N hydrochloric acid, extracted with methylene chloride. The organic phase use washed with saturated brine, dried over anhydrous sodium sulfate, filtered under reduced pressure to spin the solvent was purified by column chromatography (ethylacetate / petroleum = 1/5, v / v), to give the desired product 5 With C34H31FeNO2 in toluene, T= 0 °C , Inert atmosphere, Overall yield = 90 percent; Overall yield = 134.8 mg; Optical yield = 86 percent ee Patent; Shanghai Institute of Organic Chemistry; You, Shuli; Gao, Dewei; Gu, Qing; (36 pag.); CN105254682; (2016); (A) Chinese View in Reaxys 7 : 4.2.6.Typical procedure for the addition of diethylzinc to aldehydes using MeO-PEG-supported ferrocene 12 General procedure: Chiral ligand 12 (0.005mmol) was placed in a dried Schlenk tube under a nitrogen atmosphere. Freshly distilled toluene (2.0mL) was then added followed by diethylzinc (2.0mL, 1M in hexane). The resulting solution was cooled to 0°C and stirred for approximately 30min. The aldehyde (0.5mmol) was then added and the reaction mixture was stirred for 48h. The reaction was quenched with saturated ammonium chloride solution (4.0mL). The mixture was then extracted with diethyl ether, and the organic portion was washed with saturated aqueous NaCl. The combined organics were then dried over anhydrous MgSO4 and concentrated in vacuo. The crude compound was purified by flash chromatography to give the final product. 4.2.7 1Phenylpropan-1-ol 14a (0019) 99percent yield, 88percent ee, [η]D 20=+27.7 (c 2.2, CHCl3), [Determined by HPLC analysis Chiralcel OD-H column, Hexane/i-PrOH=100/2, Flow rate: 1mL/min, UV detection at 254nm, Retention time: tmajor=13.31min, tminor=17.24min];

5H);

13C

NMR (400MHz, CDCl3) η 0.90 (t, 3H), 1.71–1.92 (m, 2H), 1.96 (br, 1H), 4.51–4.72 (m, 1H), 7.25–7.40 (m,

NMR (100MHz, CDCl3) η 144.8, 128.4, 127.4, 126.2, 75.9, 31.9, 10.2

111/258

2018-07-03 17:29:03

Stage 1: With MeO-PEG-supported chiral ferrocenyl oxazoline carbinol ligand in hexane, toluene, Time= 0.5h, T= 0 °C , Schlenk technique, Inert atmosphere Stage 2: in hexane, toluene, Time= 48h, T= 0 °C , Schlenk technique, Inert atmosphere, Temperature, Overall yield = > 99 percent; enantioselective reaction Zhao, Wen-Xian; Liu, Guan-Jun; Wang, Jingjing; Li, Feng; Liu, Lantao; Tetrahedron Asymmetry; vol. 27; nb. 22-23; (2016); p. 1133 - 1144 View in Reaxys 7 :General procedure: To the ether solution (5 mL) of the chiral silane compound (II-f) (0.2 mmol) prepared in Example 6, tetraisopropyl titanium (2 mmol) was added, and the mixture was stirred under a nitrogen atmosphere for half an hour,(3 was added diethylzinc and stirred for half an hour, then benzaldehyde was added and stirred at room temperature for 12 hoursThe reaction was terminated; 5 mL of hydrochloric acid (1 mol / L) was added to terminate the reaction, and the reaction mixture was extracted three times with ether (5 mL)The organic phases were combined and washed with saturated aqueous sodium chloride (5 mL), dried over anhydrous sodium sulfate, filtered and the filtrate concentrated in vacuoThe crude product was separated and purified by silica gel column chromatography using ethyl acetate and petroleum ether as the eluent.The yield of the product (IV) was 80percent, eepercent = 85percent. The product was eluted with the eluent of the product, the solvent was distilled off from the eluent and recrystallized from isopropanol. The (II-f) change to (II-a), (II-b), (II-c), (II-d), (II-e),dosage equally are 0.2mmol, The other conditions were the same to obtain the target product (IV). Stage 1: With titanium(IV) isopropylate, C23H22F2O3Si in diethyl ether, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: in diethyl ether, Time= 12h, T= 20 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 89 percent Patent; Hangzhou Normal University; Li, Li; Xu, Liwen; Lu, Xing; Yang, Kefang; Zheng, Zhanjiang; Deng, Wenhui; (14 pag.); CN103396429; (2016); (B) Chinese View in Reaxys With C17H21N2NiO3 in acetonitrile, Time= 12h, T= 0 °C , Schlenk technique, Solvent, Overall yield = 74 percent; enantioselective reaction Escorihuela, Jorge; Burguete, M. Isabel; Ujaque, Gregori; Lledós, Agustí; Luis, Santiago V.; Organic and Biomolecular Chemistry; vol. 14; nb. 47; (2016); p. 11125 - 11136 View in Reaxys 4.4. General procedure for enantioselective alkylations General procedure: To the appropriate amount of chiral ligand (0.15–0.01 mmol) and aldehyde (1 mmol) under an inert atmosphere, 4 mL of dry solvent were added. The temperature of the reaction mixture was lowered to 0 C and diethylzinc (2 mmol, 2 mL, as a 1 M hexane solution) was added. The reaction was stirred for 10 min at 0 C and then at the required temperature for the required time. Subsequently, a saturated ammonium chloride solution (1 mL) was added, followed by 2 M HCl (1 mL) and the reaction mixture was extracted with diethyl ether. The joint organic phases were washed with water and brine, and dried over anhydrous sodium sulfate. The resulting solution was analyzed by GC on a chiral η-cyclodextrin capillary column in order to determine the er of the products. With (1R,3S)-N,N'-bis(2-methoxybenzyl)-1,3-diamino-1,2,2-trimethylcyclopentane in hexane, cyclohexane, Time= 24h, T= 0 20 °C , Inert atmosphere, Schlenk technique, Catalytic behavior, Reagent/catalyst, Solvent, Time, Overall yield = > 99 percentChromat.; enantioselective reaction Serra, M. Elisa Silva; Murtinho, Dina; Paz, Victória; Tetrahedron Asymmetry; vol. 28; nb. 2; (2017); p. 381 - 386 View in Reaxys 4.6. Asymmetric addition reaction of diethylzinc to benzaldehyde catalyzed by enantiopure 1 To a solution of 1 (0.1 mmol) in dry toluene (1.5 mL) was added Et2Zn (0.77 M hexane solution, 3.25 mL, 2.50 mmol) dropwise at 0 °C under N2 atmosphere, and the mixture was stirred for 30 min. A solution of benzaldehyde (106 mg, 1.00 mmol) in dry toluene (2.0 mL) was added dropwise to the mixture and the reaction mixture was stirred for 24 h at °0 C. The reaction was quenched by the addition of 1N HCl aq (5 mL) and water (20 mL). The aqueous layer was extracted with EtOAc (20 mL3). The extracts was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by preparative scale TLC (hexane/EtOAc 7:3) and its enantiopurity was determined by an HPLC analysis (Daicel ChiralPak OD-3, hexane/2-propanol 9:1,1.0 mL min-1, tr(R)=11.8 min; tr(S)=13.4 min). Stage 1: With 2-[(1S)-1-aminoethyl]phenol in hexane, toluene, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, Time= 24h, T= 0 °C , Reagent/catalyst, Overall yield = 26 percent; enantioselective reaction Kodama, Koichi; Hayashi, Naoki; Yoshida, Yasuhiko; Hirose, Takuji; Tetrahedron; vol. 72; nb. 10; (2016); p. 1387 - 1394 View in Reaxys

112/258

2018-07-03 17:29:03

4.6. Asymmetric addition reaction of diethylzinc to benzaldehyde catalyzed by enantiopure 1 To a solution of 1 (0.1 mmol) in dry toluene (1.5 mL) was added Et2Zn (0.77 M hexane solution, 3.25 mL, 2.50 mmol) dropwise at 0 °C under N2 atmosphere, and the mixture was stirred for 30 min. A solution of benzaldehyde (106 mg, 1.00 mmol) in dry toluene (2.0 mL) was added dropwise to the mixture and the reaction mixture was stirred for 24 h at °0 C. The reaction was quenched by the addition of 1N HCl aq (5 mL) and water (20 mL). The aqueous layer was extracted with EtOAc (20 mL3). The extracts was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by preparative scale TLC (hexane/EtOAc 7:3) and its enantiopurity was determined by an HPLC analysis (Daicel ChiralPak OD-3, hexane/2-propanol 9:1,1.0 mL min-1, tr(R)=11.8 min; tr(S)=13.4 min). Stage 1: With (R)-1-(2-hydroxy-3,5-di-tert-butylphenyl)ethylamine in hexane, toluene, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, Time= 24h, T= 0 °C , Overall yield = 54 percent; enantioselective reaction Kodama, Koichi; Hayashi, Naoki; Yoshida, Yasuhiko; Hirose, Takuji; Tetrahedron; vol. 72; nb. 10; (2016); p. 1387 - 1394 View in Reaxys 84 %Chromat.

Stage 1: With 1,4-bis{[(1S,2R)-7,7-dimethyl-2-hydroxynorborn-1-yl]carbonyl}-1,4-diazepan-6-ol in hexane, Time= 0.5h, T= 20 °C , Inert atmosphere Stage 2: in hexane, Time= 2h, T= 20 °C , Inert atmosphere, Reagent/catalyst, enantioselective reaction Sánchez-Carnerero, Esther M.; Sandoval-Torrientes, Rafael; Urieta-Mora, Javier; Moreno, Florencio; Maroto, Beatriz L.; de la Moya, Santiago; Reactive and Functional Polymers; vol. 113; (2017); p. 23 - 30 View in Reaxys 4.16. General procedure for the reaction of aldehydes withdiethylzinc in the presence of chiral catalyst General procedure: To the respective catalyst (0.1 mmol), 1 M Et2Zn in n-hexane solution (3 mL, 3 mmol) was added under an argon atmosphere at room temperature. The reaction was stirred for 25 min at room temperature, and benzaldehyde (1 mmol) was then added to the solution, with subsequent stirring at room temperature for a further 20 h. The reaction was quenched with saturated NH4Cl solution(15 mL) and the mixture was extracted with EtOAc (2 x 20 mL). The combined organic phase was washed with H2O (10 mL), dried (Na2SO4) and evaporated under vacuum. The crude secondary alcohols obtained were purified by flash column chromatography (n-hexane/EtOAc = 4/1). The ee and absolute configuration of the resulting material were determined by chiral GC, using a chiral stationary phase (Chirasil-Dex CB column) at 90 °C.33,34 Stage 1: With (1R,2S,3S,5R)-2-benzylaminomethyl-6,6-dimethyl-3-methylaminobicyclo[3.1.1]heptan-2-ol in hexane, Time= 0.416667h, T= 20 °C , Inert atmosphere Stage 2: in hexane, Time= 20h, T= 20 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 77 percent; enantioselective reaction Gonda, Tímea; Balázs, Attila; Tóth, Gábor; Fülöp, Ferenc; Szakonyi, Zsolt; Tetrahedron; vol. 73; nb. 18; (2017); p. 2638 2648 View in Reaxys 4.16. General procedure for the reaction of aldehydes withdiethylzinc in the presence of chiral catalyst General procedure: To the respective catalyst (0.1 mmol), 1 M Et2Zn in n-hexane solution (3 mL, 3 mmol) was added under an argon atmosphere at room temperature. The reaction was stirred for 25 min at room temperature, and benzaldehyde (1 mmol) was then added to the solution, with subsequent stirring at room temperature for a further 20 h. The reaction was quenched with saturated NH4Cl solution(15 mL) and the mixture was extracted with EtOAc (2 x 20 mL). The combined organic phase was washed with H2O (10 mL), dried (Na2SO4) and evaporated under vacuum. The crude secondary alcohols obtained were purified by flash column chromatography (n-hexane/EtOAc = 4/1). The ee and absolute configuration of the resulting material were determined by chiral GC, using a chiral stationary phase (Chirasil-Dex CB column) at 90 °C.33,34 Stage 1: With (1R,2S,3S,5R)-3-amino-2-benzylaminomethyl-6,6-dimethylbicyclo[3.1.1]heptane-2-ol in hexane, Time= 0.416667h, T= 20 °C , Inert atmosphere Stage 2: in hexane, Time= 20h, T= 20 °C , Inert atmosphere, Catalytic behavior, Reagent/catalyst, Overall yield = 87 percent; enantioselective reaction Gonda, Tímea; Balázs, Attila; Tóth, Gábor; Fülöp, Ferenc; Szakonyi, Zsolt; Tetrahedron; vol. 73; nb. 18; (2017); p. 2638 2648 View in Reaxys Asymmetric addition of diethylzinc to benzaldehyde General procedure: The corresponding amine 12-22 (0.1ηmmol) and toluene (10ηmL) were placed in a round bottomed flask. To ensure dryness, 5ηmL of toluene were distilled off. The solution was cooled to 0η°C and diethylzinc solution (1.0ηM in hexane, 3ηmmol) was added under argon. After the complete precipitation of an amorphous white solid, benzaldehyde (1ηmmol) was add-

113/258

2018-07-03 17:29:03

ed at 0η°C and the mixture was stirred at room temperature overnight. Then, a 5percent aqueous solution of hydrochloric acid was added, layers were separated and the aqueous phase was extracted with diethyl ether (4η10 mL). The combined organic layers were washed with brine (10 mL) and dried over anhydrous MgSO4. The solvents were evaporated in vacuo to afford acrude (S)-1-phenyl-1-propanol, which was purified via column chromatography (silica gel, hexane with ethyl acetate in gradient 95:5). Yield and enantiomeric excess values are listed in Table 4 (S)-1-Phenyl-1-propanol: Yellow oil; 1H NMR (600MHz, CDCl3) η: 0.96 (t, 3H, J=7.4Hz), 1.72-1.91 (m, 2H), 1.94 (s, 1H), 4.63 (t, 1H, J=6.6Hz), 7.29-7.40 (m, 5H) ppm; ee determination conditions: Chiralcel OD-H, hexane:iPrOH=98/2, flow=0.7mL/min, retention time: 19.7min (minor), 23.5min (major). Stage 1: With (R)-N,N-dimethyl-1-(1-tritylaziridin-2-yl)methanamine in hexane, toluene, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, T= 0 - 20 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 82 percent; enantioselective reaction Jarzyński, Szymon; Leśniak, Stanisław; Rachwalski, Michał; Tetrahedron Asymmetry; vol. 28; nb. 12; (2017); p. 1808 1816 View in Reaxys With 1-{(R,R’)-bis-[2-(N-benzyl-N-methylamino)-3-hexanoate propyl]dissulfide}-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)amide in toluene, Time= 72h, T= 0 °C , Schlenk technique, Inert atmosphere, Ionic liquid, Reagent/catalyst, Overall yield = 78 percent; enantioselective reaction Ferrari Bach, Mariana; Herzer Griebeler, Cassiana; Gross Jacoby, Caroline; Schneider, Paulo Henrique; European Journal of Organic Chemistry; vol. 2017; nb. 46; (2017); p. 6997 - 7004 View in Reaxys General Procedure for Enantioselective 1,2-addition of diethylzinc to aldehydes (S)-()-1-Phenylpropan-1-ol (14a). An oven-dried 10 mL Schlenk tube, equipped with amagnetic stir bar, was charged with the HAROL ligand 12i (11.5 mg, 25 μmol, 5 molpercent). Thetube was capped with a glass stopper, evacuated for 15 minutes, backfilled with dry N2,and the glass stopper was replaced with a rubber septum under positive pressure of N2. 12iwas dissolved by the addition of anhydrous hexane (2 mL) and the solution was cooled to 0 °C. Ti(OiPr)4 (222 L,213 mg, 0.75 mmol, 1.50 equiv) was added at 0°C, whereupon the solution turned light green and the mixture wasstirred at 0 °C for 30 minutes. Then 0.90 mL of 1.0 M solution of Et2Zn in hexanes (0.9 mmol, 1.80 equiv of Et2Zn)were dropwise added to the mixture and it was stirred at 0 °C for further 30 minutes. After the reaction mixturewas cooled down to -20 °C in an acetone-dry ice bath, benzaldehyde (13a) (51 L, 53 mg, 0.5 mmol, 1.00 equiv)was added. After stirring the reaction mixture at -20 °C for 2 h under N2, it was quenched with saturated aqueousNH4Cl solution (2 mL), extracted with EtOAc (230 mL). The combined organic extracts were dried over Na2SO4,filtered, and concentrated by rotary evaporation in vacuo. After purification by flash column chromatography onsilica gel (hexanes/EtOAc, 9:1), the title compound (14a) (66 mg, 485 μmol, 97percent) was obtained as a colorless oil,in 83percent ee TLC: Rf = 0.18 (silica gel; hexanes/EtOAc, 9:1 ). [] = -28 (c = 0.5, CHCl3). GC: CP-Chirasil-Dex CB, 25m, 0.25 mm ID, 0.25 μm film tickness; 190 °C inlet (split modus); 195 °C detector (FID); He, 2.0 mL/min (constantflow modus); 80 °C (4 min), 10 °C/min, 110 °C (42 min), 10 °C/min, 180 °C (4 min) ; tR = 21.48 min (ent-14a), tR =22.06 min (14a). FTIR (KBr): max (cm-1) = 3368 (s), 2965 (s), 2933 (s), 2876 (s), 1948 (w), 1809 (w), 1603 (w),1493 (s), 1453 (s), 1331 (w), 1201 (w), 1096 (w), 1014 (w), 974 (w), 763 (w), 700 (s), 545 (w). 1H NMR (500MHz, CDCl3): = 0.89 (t, J = 7.4 Hz, 3H), 1.76–1.68 (m, 1H), 1.85–1.76 (m, 1H), 2.13 (s, 1H), 4.55 (t, J = 6.6 Hz, 1H),7.29–7.23 (m, 1H), 7.36–7.29 (m, 4H). 13C NMR (125 MHz, CDCl3): = 10.1 (CH3), 31.8 (CH2), 75.9 (CH), 125.9(CH), 127.4 (CH), 128.3 (CH), 144.6 (C). GCMS: tR = 19.52 min, m/z (percent) = 136 ([M]+, 14), 117 (7), 107 (100), 91(7), 79 (71), 51 (10). Stage 1: With titanium(IV) isopropylate, (1S,2R)-(-)-2-(2-hydroxy-3,5-bis(2-phenylpropan-2-yl)phenyl)indan-1-ol in hexane, Time= 0.5h, T= 0 °C , Schlenk technique, Inert atmosphere Stage 2: in hexane, Time= 2h, T= -20 °C , Schlenk technique, Inert atmosphere, Catalytic behavior, Reagent/catalyst, Solvent, Temperature, Overall yield = 97 percent; Overall yield = 66 mg; enantioselective reaction Dilek, Ömer; Tezeren, Mustafa A.; Tilki, Tahir; Ertürk, Erkan; Tetrahedron; vol. 74; nb. 2; (2018); p. 268 - 286 View in Reaxys With (1R,2R,3S,5R)-6,6-dimethyl-2-(3-phenyl-1,2,4-oxadiazol-5-yl)bicyclo[3.1.1]heptane-2,3-diol in hexane, Catalytic behavior, Reagent/catalyst, enantioselective reaction Gonda, Tímea; Bérdi, Péter; Zupkó, István; Fülöp, Ferenc; Szakonyi, Zsolt; International Journal of Molecular Sciences; vol. 19; nb. 1; (2018); Art.No: 81 View in Reaxys Stage 1: With (E,4R,5S)-N-allyl-5-cyclohexyl-5-hydroxy-4-( piperidin-1-yl)pent-2-enamide in toluene, Time= 0.333333h, T= 20 °C , Inert atmosphere Stage 2: in hexane, toluene, Time= 6h, T= 20 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 84 percent; enantioselective reaction

114/258

2018-07-03 17:29:03

Sappino, Carla; Mari, Alessandra; Mantineo, Agnese; Moliterno, Mauro; Palagri, Matteo; Tatangelo, Chiara; Suber, Lorenza; Bovicelli, Paolo; Ricelli, Alessandra; Righi, Giuliana; Organic and Biomolecular Chemistry; vol. 16; nb. 11; (2018); p. 1860 - 1870 View in Reaxys 3.4. General Procedure for the Reaction of Aldehydes with Diethylzinc in the Presence of Chiral Catalyst To the respective catalyst (0.1 mmoL), 1 M Et2Zn in n-hexane solution (3 mL, 3 mmoL) was addedunder an Ar atmosphere at room temperature. The reaction was stirred for 25 min at room temperature(see Table 1), and benzaldehyde (1 mmoL) was then added to the solution with subsequent stirring atroom temperature (see Table 1) for a further 20 h. The reaction was quenched with a saturated NH4Clsolution (15 mL), and the mixture was extracted with EtOAc (2 20 mL). The combined organic phasewas washed with H2O (10 mL), dried (Na2SO4), and evaporated under vacuum. The crude secondaryalcohols obtained were purified by flash column chromatography (Rf = 0.54; n-hexane/EtOAc = 4/1).The ee and absolute configuration of the resulting material were determined by chiral HPLC analysis ona Chiralcel OD-H column and the data are as follows: 1-phenyl-1-propanol; V(nhexane)/V(2-propanol)= 95: 5, 0.7 mL/min, 215 nm, tR1 = 6.29 min for R-isomer, tR2 = 6.73 min for S-isomer [7]. Stage 1: With 2-((benzylamino)methyl)-5-isopropylbicyclo[3.1.0]hexane-2,3-diol in hexane, Time= 0.416667h, T= 20 °C , Inert atmosphere Stage 2: in hexane, Time= 20h, T= 20 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 98 percent Tashenov, Yerbolat; Daniels, Mathias; Robeyns, Koen; Van Meervelt, Luc; Dehaen, Wim; Suleimen, Yerlan M.; Szakonyi, Zsolt; Molecules; vol. 23; nb. 4; (2018); Art.No: Y View in Reaxys Enantioselective Addition of Diethylzinc to Aldehydes General procedure: The ligand 7 (0.10 mmol) was dissolved in anhyd toluene (1 mL) in a test tube. The solution was stirred for 5 min. A 1.0 M solution of Et2Zn in n-hexane (2.0 mmol, 2.0 mL) was then added, and after the mixture had been stirred for 5 min at the appropriate temperature, a solution of aldehyde (1.0 mmol) in anhyd toluene (1 mL) was added by syringe. The mixture was stirred for the time reported in Table 2. Sat. aq NH4Cl (10 mL) was added and the mixture was extracted with EtOAc (3 × 10 mL). The collected organic phases were combined, washed with H2O, dried (Na2SO4), and concentrated. GC or HPLC analysis was done after suitable dilution. General method for GC analysis: TInj: 260 °C, TDet: 260 °C (FID), H2: 1 mL/min, split 100:1. Stage 1: With (1R,3S)-1-benzyl-6,7-dimethoxy-3-[(5R)-4-methoxy-6-methyl-5,6,7,8-tetrahydro[1,3]dioxolo[4,5-g]isoquinolin-5-yl]-1,3-dihydro-2-benzofuran-1-ol in hexane, toluene, Time= 0.0833333h, T= 20 °C Stage 2: in hexane, toluene, Time= 3h, T= 20 °C , Catalytic behavior, Reagent/catalyst, Temperature, enantioselective reaction Mohebbi, Maryam; Bararjanian, Morteza; Ebrahimi, Samad N.; Smieško, Martin; Salehi, Peyman; Synthesis (Germany); vol. 50; nb. 9; (2018); p. 1841 - 1848; Art.No: SS-2017-N0571-OP View in Reaxys

H OH

Rx-ID: 3399327 View in Reaxys 3/176 Yield 100 %

Conditions & References With magnesium chloride in isopropyl alcohol, T= 25 °C , pH= 7, Catalytic behavior Benítez-Mateos, Ana I.; San Sebastian, Eneko; Ríos-Lombardía, Nicolás; Morís, Francisco; González-Sabín, Javier; López-Gallego, Fernando; Chemistry - A European Journal; vol. 23; nb. 66; (2017); p. 16843 - 16852 View in Reaxys

99 %

With potassium tert-butylate, hydrogen, [bis(2-methylallyl)cycloocta-1,5-diene]ruthenium(II), (R)-Ph-BINAN-H-Py in isopropyl alcohol, Time= 18h, T= 25 °C , p= 38000Torr Huang, Hanmin; Okuno, Tomoko; Tsuda, Kazuomi; Yoshimura, Masahiro; Kitamura, Masato; Journal of the American Chemical Society; vol. 128; nb. 27; (2006); p. 8716 - 8717 View in Reaxys

99 %

With dimethylsulfide borane complex, (1R)-1-phenyl-N-(((S)-pyrrolidin-2-yl)methyl)ethanamine in toluene, Time= 8h, T= -78 °C , optical yield given as percent ee, enantioselective reaction Luis Olivares-Romero; Juaristi, Eusebio; Tetrahedron; vol. 64; nb. 42; (2008); p. 9992 - 9998

115/258

2018-07-03 17:29:03

View in Reaxys 99 %

With bis(1,5-cyclooctadiene)diiridium(I) dichloride, C45H58NP, potassium tert-butylate, hydrogen in propan-1-ol, Time= 1.5h, T= 25 - 30 °C , p= 4560.31Torr , Autoclave, optical yield given as percent ee, enantioselective reaction Xie, Jian-Bo; Xie, Jian-Hua; Liu, Xiao-Yan; Zhang, Qian-Qian; Zhou, Qi-Lin; Chemistry - An Asian Journal; vol. 6; nb. 3; (2011); p. 899 - 908 View in Reaxys

99 %

With C32H31N2O8RuS3 (2-)*2Na(1+), sodium formate in water, Time= 12h, T= 40 °C , Inert atmosphere, enantioselective reaction Li, Jiahong; Li, Xuefeng; Ma, Yaping; Wu, Jiashou; Wang, Fei; Xiang, Jing; Zhu, Jin; Wang, Qiwei; Deng, Jingen; RSC Advances; vol. 3; nb. 6; (2013); p. 1825 - 1834 View in Reaxys

99 %

1.4. Enantioselective borane reduction of ketones General procedure: BH3·SMe2 (2.0 M in toluene, 250 μL, 500 μmol) was added to a solution of the B-alkoxy oxazaborolidine 8 (7.43 mg, 25.0 μmol in toluene (1 mL), prepared prior to use according to procedure 1.2.6). After 15 min at 50 °C, the reaction mixture was adjusted to 20 °C and a solution of acetophenone (1a, 60.1 mg, 58.3 μL, 500 μmol) in toluene (1 mL) was continuously introduced over a period of 60 min via syringe pump. After addition, the reaction was stirred for additional 10 min and quenched with methanolic H2SO4 (1.1 M, 500 μL). The mixture was stirred for further 15 min and directly subjected to column chromatography (SiO2, pentane/Et2O 2:1) to give (R)-phenylethanol ((R)-2a, 58.3 mg, 477 μmol, 95percent, 97percent ee) as a colorless oil. With dimethylsulfide borane complex, (2aS,4aR)-2,2-diphenylhexahydro-2H-1,7-dioxa-7b-aza-7a-boracyclopenta[cd]indene in toluene, Time= 1.16667h, T= 20 °C , Inert atmosphere, enantioselective reaction Kaldun, Johannes; Krimalowski, Alexander; Breuning, Matthias; Tetrahedron Letters; vol. 57; nb. 23; (2016); p. 2492 2495 View in Reaxys

99 %

With bis(1,5-cyclooctadiene)diiridium(I) dichloride, (SC,SC,RFC)-1-(diphenylphosphino)-2-[1-N-((4S)-4-tert-butyl-2-oxazolinyl-2-ylmethyl)ethyl]ferrocene, hydrogen, potassium carbonate in isopropyl alcohol, Time= 2h, T= 25 °C , p= 15201Torr , Glovebox, Autoclave, enantioselective reaction Wu, Weilong; Liu, Shaodong; Duan, Meng; Tan, Xuefeng; Chen, Caiyou; Xie, Yun; Lan, Yu; Dong, Xiu-Qin; Zhang, Xumu; Organic Letters; vol. 18; nb. 12; (2016); p. 2938 - 2941 View in Reaxys

99%

With bis(1,5-cyclooctadiene)diiridium(I) dichloride, C46H66FeNO2P, hydrogen, lithium tert-butoxide in isopropyl alcohol, Time= 6h, T= 25 - 30 °C , p= 15201Torr , Inert atmosphere, Autoclave, enantioselective reaction Yu, Jianfei; Long, Jiao; Yang, Yuhong; Wu, Weilong; Xue, Peng; Chung, Lung Wa; Dong, Xiu-Qin; Zhang, Xumu; Organic Letters; vol. 19; nb. 3; (2017); p. 690 - 693 View in Reaxys

98 %

With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer, (1R,2R)-9-oxo-9H-fluorene-2,7-disulfonic acid bis-[(2-aminocyclohexyl)amide], sodium formate in water, Time= 0.25h, T= 40 °C , optical yield given as percent ee, enantioselective reaction Montalvo-Gonzalez, Ruben; Chavez, Daniel; Aguirre, Gerardo; Parra-Hakea, Miguel; Somanathan, Ratnasamy; Journal of the Brazilian Chemical Society; vol. 21; nb. 3; (2010); p. 431 - 435 View in Reaxys

96 %

With potassium tert-butylate, hydrogen, {R-4-(3,5-Xyl)2P-12-Ph2P[2.2]paracyclophane}RuCl2(S,S)-DPEN in isopropyl alcohol, Time= 1.5h, T= 25 °C , p= 3750.38 - 7500.75Torr Cheemala, Murthy N.; Gayral, Maud; Brown, John M.; Rossen, Kai; Knochel, Paul; Synthesis; nb. 24; (2007); p. 3877 3885 View in Reaxys

96 %

With (2-((2,4-dimethyl-5-phenylimidazo[1,5-b]pyridazin-7-yl)amido)-4-methylpentan-1-ol)(1,5-cyclooctadiene)iridium(I), potassium tert-butylate, hydrogen, acetone in tetrahydrofuran, Time= 48h, T= 20 °C , p= 15.0015Torr , Autoclave, optical yield given as percent ee, enantioselective reaction

116/258

2018-07-03 17:29:03

Irrgang, Torsten; Friedrich, Denise; Kempe, Rhett; Angewandte Chemie - International Edition; vol. 50; nb. 9; (2011); p. 2183 - 2186 View in Reaxys 95 %

With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer, C22H32N4O4S2, water, sodium formate, Time= 0.25h, T= 40 °C , Air atmosphere, optical yield given as percent ee, enantioselective reaction Montalvo-Gonzalez, Ruben; Chavez, Daniel; Aguirre, Gerardo; Parra-Hake, Miguel; Somanathan, Ratnasamy; Synthetic Communications; vol. 39; nb. 15; (2009); p. 2737 - 2746 View in Reaxys

95 %

With Ir-SpiroPAP, potassium tert-butylate in ethanol, Time= 10h, T= 40 °C , Inert atmosphere Liu, Wei-Peng; Yuan, Ming-Lei; Yang, Xiao-Hui; Li, Ke; Xie, Jian-Hua; Zhou, Qi-Lin; Chemical Communications; vol. 51; nb. 28; (2015); p. 6123 - 6125 View in Reaxys

95 %

With C48H66FeN6P2 (2+)*2BF4 (1-), sodium t-butanolate in isopropyl alcohol, Time= 2.5h, T= 60 °C , Glovebox, Schlenk technique, Reagent/catalyst, Temperature, enantioselective reaction Bigler, Raphael; Huber, Raffael; Mezzetti, Antonio; Angewandte Chemie - International Edition; vol. 54; nb. 17; (2014); p. 5171 - 5174; Angew. Chem.; vol. 127; nb. 17; (2014); p. 5260 - 5263,4 View in Reaxys

94 %

General procedure for the borane reduction of prochiral ketones General procedure: To a solution of the corresponding catalyst 3-8 (0.1-0.01 mmol) in dry THF (3 mL), BH3*SMe2 (10 M, 100 μL, 1 mmol) was added at room temperature with stirring. Next, a solution of ketone (1 mmol) in THF (2 mL) was added at a rate of 3 mL per hour using a syringe pump. The solution was stirred for 20 min and quenched by the addition of MeOH (1 mL) at room temperature. After stirring for 30 min at rt, the solvents were evaporated under vacuum and the product was isolated by column chromatography using hexane/EtOAc (4:1) as eluent. Stage 1: With dimethylsulfide borane complex, C12H22BNO3 in tetrahydrofuran, T= 20 °C Stage 2: With methanol in tetrahydrofuran, Time= 0.5h, T= 20 °C , optical yield given as percent ee, enantioselective reaction Krzeminski, Marek P.; Cwiklinska, Marta; Tetrahedron Letters; vol. 52; nb. 30; (2011); p. 3919 - 3921 View in Reaxys

94 %

With C38H38IrN4S2 (1+)*F6P(1-), ammonium formate, 3-methyl-5-p-methoxyphenyl-1-hydropyrazole in tetrahydrofuran, water, Time= 10h, T= 60 °C , enantioselective reaction Tian, Cheng; Gong, Lei; Meggers, Eric; Chemical Communications; vol. 52; nb. 22; (2016); p. 4207 - 4210 View in Reaxys

93 %

With dimethylsulfide borane complex in tetrahydrofuran, Time= 2h, T= 20 °C , enantioselective reaction Hosoda, Naoya; Kamito, Hideaki; Takano, Miki; Takebe, Yoshitaka; Yamaguchi, Yoshitaka; Asami, Masatoshi; Tetrahedron; vol. 69; nb. 11; (2013); p. 2509 - 2509 View in Reaxys

92 %

With C22H27Cl2CoN3O, sodium triethylborohydride, 4,4,5,5-tetramethyl-1,3,2-dioxaborolane in tetrahydrofuran, diethyl ether, Time= 2h, T= 20 °C , Inert atmosphere, enantioselective reaction Guo, Jun; Chen, Jianhui; Lu, Zhan; Chemical Communications; vol. 51; nb. 26; (2015); p. 5725 - 5727 View in Reaxys

91 %

Stage 1: With methylphenylsilane, sodium t-butanolate, (R)-BINAP-Cu(I) in toluene, Time= 18h, T= -78 °C Stage 2: With sodium hydroxide in methanol, toluene, Time= 1h, T= 20 °C Issenhuth, Jean Thomas; Dagorne, Samuel; Bellemin-Laponnaz, Stephane; Advanced Synthesis and Catalysis; vol. 348; nb. 14; (2006); p. 1991 - 1994 View in Reaxys

91 %

With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer, N-(tert-butoxycarbonyl)-L-valine-(6-O-benzoyl-1-O-benzyl-5deoxy-2,3-O-isopropylidene-5-thioamido-η-D-mannofuranose), potassium tert-butylate, lithium chloride in tetrahydrofuran, isopropyl alcohol, Time= 3h, T= 20 °C , enantioselective reaction

117/258

2018-07-03 17:29:03

Margalef, Jèssica; Slagbrand, Tove; Tinnis, Fredrik; Adolfsson, Hans; Diéguez, Montserrat; Pàmies, Oscar; Advanced Synthesis and Catalysis; vol. 358; nb. 24; (2016); p. 4006 - 4018 View in Reaxys 90 %

General procedure for transferhydrogenation General procedure: In a Schlenk tube under an argon atmosphere, the corresponding metal complex (0.5 or 5 mol percent) is dissolved in 0.1 mL of iso-propanol. A solution of KOH in iso-propanol (40mL, 0.1 M) is then added via syringe. An immediate color change occurs throughout the addition, and a solution of acetophenone (0.2 mmol) in iso-propanol (1.9 mL) is then added. The mixture is stirred at room temperature overnight. The reaction is quenched by addition of an aqueous solution of HCl (10percent), and the mixture is extracted with CH2Cl2 (3x). The combined organic phases are dried over Na2SO4, filtrated over Celite and the solvent is removed under reduced pressure. The crude mixture is purified by chromatography (silicagel, n-hexane/ ethyl acetate, 4/1, v/v) to obtain the desired secondary alcohol. With C38H49N3O4RuS2, potassium hydroxide in isopropyl alcohol, Time= 12h, T= 25 °C , Inert atmosphere, Noyori Asymmetric Hydrogenation, Reagent/catalyst, enantioselective reaction Romero, R. Martín; Fra, Laura; Lishchynskyi, Anton; Martínez, Claudio; Streuff, Jan; Muñiz, Kilian; Tetrahedron; vol. 71; nb. 26-27; (2015); p. 4465 - 4472 View in Reaxys

90 %

Bioreduction of 1a-o by using Lactobacillus reuteri restingcells General procedure: L. reuteri strains were grown in MRS medium. This pre-culture was inoculated in 500 mL of MRS and incubated for 24 h (37° C). Cells were harvested by centrifugation (2800 × g, 10 min)and washed twice with phosphate buffered saline pH 7.4 (PBS,Sigma–Aldrich). Then the cells were suspended in the same bufferand adjusted for cell density. To this cell suspension, 1percent glucose and the desired concentration of arylketone were added (total volume50 mL). To ensure the anaerobic conditions, flasks were degassed with a N2flux for 3 min. The reaction mixture was incubated at 37° C, 200 rpm. Sugars and organic acids were analyzed by HPLCbefore the extraction of the bioconversion products. The reactions progress was monitored by collecting suspension aliquots in a timecourse: after extraction with diethyl ether, the organic phase wasanalyzed by NMR or HPLC. After the appropriate conversion time(see Table 3), the suspension was centrifuged (2800 × g, 10 min,4C), and the aqueous phase was extracted with diethyl ether(3 × 15 mL). The organic phase was dried over Na2SO4, filtered, andevaporated under reduced pressure. The product was isolated bysilica gel column chromatography using hexane and ethyl acetate(90:10 or 80:20) as eluents to yield the desired alcohols (2a-o,Table 2). Absolute configurations of alcohols 2a-o obtained from the bioprocess were determined by comparison of their optical spe-cific rotation signs and/or retention times with known data (See Supporting informations). With D-glucose in aq. phosphate buffer, Time= 24h, T= 37 °C , Microbiological reaction, Inert atmosphere, Green chemistry, Time, enantioselective reaction Perna; Ricci; Scilimati; Mena; Pisano; Palmieri; Agrimi; Vitale; Journal of Molecular Catalysis B: Enzymatic; vol. 124; (2016); p. 29 - 37 View in Reaxys

90 %

With formic acid, C37H38ClN2O2RhS, triethylamine in neat (no solvent), Time= 22h, T= 24 - 30 °C , Inert atmosphere, Reagent/ catalyst, enantioselective reaction Zheng, Long-Sheng; Llopis, Quentin; Echeverria, Pierre-Georges; Férard, Charlène; Guillamot, Gérard; Phansavath, Phannarath; Ratovelomanana-Vidal, Virginie; Journal of Organic Chemistry; vol. 82; nb. 11; (2017); p. 5607 - 5615 View in Reaxys

87 %

With copper(l) chloride, sodium t-butanolate, (R)-3,5-xyl-MeO-BIPHEP in toluene, Time= 48h, T= -78 °C Lipshutz; Noson; Chrisman; Journal of the American Chemical Society; vol. 123; nb. 51; (2001); p. 12917 - 12918 View in Reaxys

86 %

Stage 1: With silver tetrafluoroborate, diethoxymethylane, C30H39ClIrN3O2 in tetrahydrofuran, Time= 15h, T= 20 °C Stage 2: With potassium carbonate in tetrahydrofuran, methanol, Time= 2h, T= 20 °C , enantioselective reaction Shinohara, Kanako; Kawabata, Shun; Nakamura, Hanako; Manabe, Yoshiki; Sakaguchi, Satoshi; European Journal of Organic Chemistry; vol. 2014; nb. 25; (2014); p. 5532 - 5539 View in Reaxys

85 %

With tris(triphenylphosphine)ruthenium(II) chloride, Phospherox, potassium isopropoxide, isopropyl alcohol, Time= 1h, T= 50 °C Sammakia, Tarek; Stangeland, Eric L.; Journal of Organic Chemistry; vol. 62; nb. 18; (1997); p. 6104 - 6105

118/258

2018-07-03 17:29:03

View in Reaxys 85 %

With borane-THF, 1,1'-(diphenylamine-2,2'-dicarbonyl)-bis[(2S)-η,η-diphenyl-2-pyrrolidinemethanol] in tetrahydrofuran, cyclohexane, Time= 3h, T= 50 °C , optical yield given as percent ee, enantioselective reaction Wang, Jin; Liu, Han; Du, Da-Ming; Tetrahedron Asymmetry; vol. 20; nb. 5; (2009); p. 605 - 609 View in Reaxys

83 %

With [RhCl2(p-cymene)]2, sodium formate in water, Time= 15h, T= 20 - 40 °C , enantioselective reaction Sarkar, Shaheen M.; Yusoff, Mashitah Mohd; Rahman, Md. Lutfor; Journal of the Chinese Chemical Society; vol. 62; nb. 2; (2015); p. 177 - 181 View in Reaxys

78 %

With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer, C31H40N2O8S, sodium isopropylate, lithium chloride in tetrahydrofuran, isopropyl alcohol, Time= 3h, T= 20 °C , Inert atmosphere, Schlenk technique, Reagent/catalyst, enantioselective reaction Coll, Mercè; Pàmies, Oscar; Diéguez, Montserrat; Advanced Synthesis and Catalysis; vol. 356; nb. 10; (2014); p. 2293 - 2302 View in Reaxys

71 %

Stage 1: With Triethoxysilane, (S,E)-(+)-2,6-diisopropyl-N-(2-((2-(4-phenyl-4,5-dihydrooxazol-2-yl)phenyl)amino)benzylidene)aniline, sodium triethylborohydride, cobalt(II) chloride in tetrahydrofuran, dichloromethane, Time= 15h, T= 20 °C , Schlenk technique, Inert atmosphere Stage 2: With potassium carbonate in tetrahydrofuran, methanol, dichloromethane, Time= 2h, T= 20 °C , Schlenk technique, Inert atmosphere, enantioselective reaction Chen, Xu; Lu, Zhan; Organic Letters; vol. 18; nb. 18; (2016); p. 4658 - 4661 View in Reaxys

60 %

With D-glucose, Bacillus megaterium glucose dehydrogenase, Pichia glucozyma CBS 5766 recombinant NADPH-dependent benzil reductase, NADPH in dimethyl sulfoxide, Time= 24h, T= 25 °C , pH= 8, Enzymatic reaction, enantioselective reaction Contente, Martina Letizia; Serra, Immacolata; Brambilla, Marta; Eberini, Ivano; Gianazza, Elisabetta; De Vitis, Valerio; Molinari, Francesco; Zambelli, Paolo; Romano, Diego; Applied Microbiology and Biotechnology; vol. 100; nb. 1; (2016); p. 193 - 201 View in Reaxys

53 %

With sodium aluminum tetrahydride, (S,S)-2,3-O-isopropylidene-1,1,4,4-tetraphenylthreitol in tetrahydrofuran, T= -20 - -18 °C Vinogradov; Gorshkova; Chel'tsova; Kurilov; Ferapontov; Shishkin; Heise; Russian Chemical Bulletin; vol. 52; nb. 8; (2003); p. 1841 - 1846 View in Reaxys

51 %

With formic acid, N-((R,R)-2-((4η-methoxy-[1,1η-biphenyl]-2-ylmethyl)amino)-1,2-diphenylethyl)-4-iodobenzenesulfonamide ruthenium(II) chloride, triethylamine, Time= 24h, T= 60 °C , Inert atmosphere, Reagent/catalyst Soni, Rina; Jolley, Katherine E.; Gosiewska, Silvia; Clarkson, Guy J.; Fang, Zhijia; Hall, Thomas H.; Treloar, Ben N.; Knighton, Richard C.; Wills, Martin; Organometallics; vol. 37; nb. 1; (2018); p. 48 - 64 View in Reaxys

44 %

With trimethoxysilane, Li(1+)*C9H12NO(1-) in tetrahydrofuran, Time= 3h, Ambient temperature Kohra, Shinya; Hayashida, Hisashi; Tominaga, Yoshinori; Hosomi, Akira; Tetrahedron Letters; vol. 29; nb. 1; (1988); p. 89 - 92 View in Reaxys

30 %

With Debaryomyces hansenii 20220 in various solvent(s) Homann, Michael J.; Vail, Robert B.; Previte, Edward; Tamarez, Maria; Morgan, Brian; Dodds, David R.; Zaks, Aleksey; Tetrahedron; vol. 60; nb. 3; (2004); p. 789 - 797 View in Reaxys

30 %

With (p-cymene)ruthenium(II) chloride, 1-butyl-3-({[(1R,2S)-1-hydroxy-1-phenylpropan-2-yl]amino}methyl)pyridin-1-ium bromide, sodium formate in water, Time= 24h, T= 40 - 50 °C , Glovebox, Schlenk technique, Inert atmosphere, Green chemistry, enantioselective reaction

119/258

2018-07-03 17:29:03

Vasiloiu, Maria; Gaertner, Peter; Zirbs, Ronald; Bica, Katharina; European Journal of Organic Chemistry; vol. 2015; nb. 11; (2015); p. 2374 - 2381 View in Reaxys 27 %

With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer, sodium formate in water, Time= 10h, T= 40 °C , Inert atmosphere, Schlenk technique, enantioselective reaction Wei, Juan; Zhang, Xiaomin; Zhang, Xiaoming; Zhao, Yaopeng; Li, Ruixiang; Yang, Qihua; ChemCatChem; vol. 6; nb. 5; (2014); p. 1368 - 1374 View in Reaxys

With Leifsonia sp. S749 cells alcohol dehydrogenase, nicotinamide adenine dinucleotide, isopropyl alcohol in phosphate buffer, Time= 24h, T= 25 °C , pH= 7.0 Inoue, Kousuke; Makino, Yoshihide; Itoh, Nobuya; Tetrahedron Asymmetry; vol. 16; nb. 15; (2005); p. 2539 - 2549 View in Reaxys With chiral oxazaborolidine derivative, T= -20.1 °C , enantioselectivity; var. asymmetric oxazaborolidines; var. ketones Jones, Deborah K.; Liotta, Dennis C.; Shinkai, Ichiro; Mathre, David J.; Journal of Organic Chemistry; vol. 58; nb. 4; (1993); p. 799 - 801 View in Reaxys With borane, methyl oxazaborolide in tetrahydrofuran, Time= 0.0833333h, T= 0 °C Corey, E. J.; Link, John O.; Tetrahedron Letters; vol. 30; nb. 46; (1989); p. 6275 - 6278 View in Reaxys With borane, oxazaborilidine compound (2) in tetrahydrofuran, Time= 0.0333333h, T= -10 °C , Yield given Corey, E. J.; Bakshi, Raman K.; Shibata, Saizo; Chen Chung-Pin; Singh, Vinod K.; Journal of the American Chemical Society; vol. 109; nb. 25; (1987); p. 7925 - 7926 View in Reaxys With chiral oxazaborolidine derivative, T= -20.1 °C Jones, Deborah K.; Liotta, Dennis C.; Shinkai, Ichiro; Mathre, David J.; Journal of Organic Chemistry; vol. 58; nb. 4; (1993); p. 799 - 801 View in Reaxys With borane-THF, (S)-η,η-diphenyl-(azetidin-2-yl)methanol in tetrahydrofuran, Time= 2h, T= 30 °C Behnen; Dauelsberg Ch.; Wallbaum; Martens; Synthetic Communications; vol. 22; nb. 15; (1992); p. 2143 - 2153 View in Reaxys With polymersupported (S)-(-)-2-amino-3-(p-hydroxyphenyl)-1,1-diphenyl-1-propanol-BH3 in tetrahydrofuran, asymmetric reduction Itsuno, Shinichi; Ito, Koichi; Maruyama, Toshihiro; Kanda, Naoki; Hirao, Akira; Nakahama, Seiichi; Bulletin of the Chemical Society of Japan; vol. 59; (1986); p. 3329 - 3331 View in Reaxys With chloro(1,5-cyclooctadiene)rhodium(I) dimer, potassium tert-butylate, (1S,2S)-N,N'-dimethyl-N,N'-di(phenycarbamyl)-1,2diphenylethylenediamine in isopropyl alcohol, Time= 168h, T= 60 °C Gamez, Patrick; Dunjic, Branko; Lemaire, Marc; Journal of Organic Chemistry; vol. 61; nb. 16; (1996); p. 5196 - 5197 View in Reaxys With dimethylsulfide, (S)-diphenyl prolinol derived oxazaborolidine, borane in tetrahydrofuran, toluene, Time= 0.25h, T= 45 °C Prasad; Joshi; Tetrahedron Asymmetry; vol. 7; nb. 11; (1996); p. 3147 - 3152 View in Reaxys

12.5E-6 mol With phosphate buffer, ADH (EC 1.1.1.2), MV2+, nicotinamide adenine dinucleotide phosphate in water, tert-butyl alcohol, Time= 30h, electrolysis; other reaction system

120/258

2018-07-03 17:29:03

Yuan, Ruo; Watanabe, Shozo; Kuwabata, Susumu; Yoneyama, Hiroshi; Journal of Organic Chemistry; vol. 62; nb. 8; (1997); p. 2494 - 2499 View in Reaxys With phosphate buffer, Pichia etchellsii CBS 2011, Time= 24h, pH= 7.0, enantioselective reduction Molinari, Francesco; Gandolfi, Raffaella; Villa, Raffaella; Occhiato, Ernesto G.; Tetrahedron Asymmetry; vol. 10; nb. 18; (1999); p. 3515 - 3520 View in Reaxys With potassium hydroxide, {2-[(RP)-methylphenylphosphinoyl]ethyl}-(1S)-(1-phenylethyl)amine, [ruthenium(II)(η6-1-methyl-4isopropyl-benzene)(chloride)(μ-chloride)]2 in isopropyl alcohol, Time= 3h, T= 20 °C , Product distribution, Further Variations: Catalysts Maj, Anna M.; Pietrusiewicz; Suisse, Isabelle; Agbossou, Francine; Mortreux, Andre; Journal of Organometallic Chemistry; vol. 626; nb. 1-2; (2001); p. 157 - 160 View in Reaxys With sodium hydroxide, Phospherox, hydrogen, tris(triphenylphosphine)ruthenium(II) chloride in toluene, Time= 1h, T= 20 °C , p= 60004.8Torr Naud, Frederic; Malan, Christophe; Spindler, Felix; Rueggeberg, Carsten; Schmidt, Andreas T.; Blaser, Hans-Ulrich; Advanced Synthesis and Catalysis; vol. 348; nb. 1-2; (2006); p. 47 - 50 View in Reaxys 91 % Chromat.

With sodium formate, [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, sulfonated chiral copolymer in water, Time= 2h, T= 40 °C Arakawa, Yukihiro; Haraguchi, Naoki; Itsuno, Shinichi; Tetrahedron Letters; vol. 47; nb. 19; (2006); p. 3239 - 3243 View in Reaxys With N-Boc-L-valine (S)-1-phenylthioamide, sodium isopropylate, dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer in isopropyl alcohol, Time= 0.5h, T= 20 °C Zaitsev, Alexey B.; Adolfsson, Hans; Organic Letters; vol. 8; nb. 22; (2006); p. 5129 - 5132 View in Reaxys With sodium formate, Ir-(R,R,R)-N-camphorsulfonyl-1,2-diphenylethylenediamine, Time= 9.5h, T= 40 °C Li, Xiaohong; Blacker, John; Houson, Ian; Wu, Xiaofeng; Xiao, Jianliang; Synlett; nb. 8; (2006); p. 1155 - 1160 View in Reaxys With triethylamine, chiral Rh/tetramethylcyclopentadienyl complex in formic acid, Time= 6h, T= 25 °C Matharu, Daljit S.; Morris, David J.; Clarkson, Guy J.; Wills, Martin; Chemical Communications; nb. 30; (2006); p. 3232 3234 View in Reaxys With HCl buffer, isopropyl alcohol, 2-amino-2-hydroxymethyl-1,3-propanediol, Time= 24h, T= 30 °C , pH= 7 Lavandera, Ivan; Hoeller, Brigitte; Kern, Alexander; Ellmer, Ursula; Glieder, Anton; de Wildeman, Stefaan; Kroutil, Wolfgang; Tetrahedron Asymmetry; vol. 19; nb. 16; (2008); p. 1954 - 1958 View in Reaxys 18 :[RuCl2(p-cymene]2 (N) (1.22 mg, 2 μmol) and a chiral diphosphonite ligand such as XI (0.010 mmol) were heated in dry isopropanol (2.5 ml) at 80° C. under argon for 1 h. Once the mixture had been cooled to room temperature, a base NaOH (0.04 mmol; 0.5 ml of a 0.08 M solution in isopropanol) or KOC(CH3)3 (0.04 mmol; 0.5 ml of a 0.08 M solution in isopropanol) were added, then a ketone such as acetophenone (0.4 mmol) was added. The reaction mixture was stirred at 40° C. under argon over a defined period (typically 16-96 h). Samples were taken from the reaction solution and put through a small amount of silica gel before the GC analysis to determine the conversions and the ee values by gas chromatography. With sodium hydroxide, isopropyl alcohol, [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, (11bR,11'bR)-4,4'-(9,9-dimethyl-9H-xanthane-4,5-diyl)bis[dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin], Time= 27h, T= 40 80 °C , Product distribution / selectivity Patent; STUDIENGESELLSCHAFT KOHLE MBH; US2008/255355; (2008); (A1) English

121/258

2018-07-03 17:29:03

View in Reaxys With C68H78Cl2N2O4P2Ru, potassium tert-butylate, hydrogen in isopropyl alcohol, Time= 8h, T= 20 - 22 °C , p= 7600.51Torr , optical yield given as percent ee, enantioselective reaction Li, Wei; Sun, Xianfeng; Zhou, Le; Hou, Guohua; Yu, Shichao; Zhang, Xumu; Journal of Organic Chemistry; vol. 74; nb. 3; (2009); p. 1397 - 1399 View in Reaxys With [Ru(II)(η6-p-cymene)(μ-Cl)Cl]2, sodium formate in water, Time= 2h, T= 40 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Arakawa, Yukihiro; Chiba, Atsuko; Haraguchi, Naoki; Itsuno, Shinichi; Advanced Synthesis and Catalysis; vol. 350; nb. 14-15; (2008); p. 2295 - 2304 View in Reaxys With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer, C21H28N2O2S, sodium isopropylate, lithium chloride in isopropyl alcohol, Time= 2h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Ahlford, Katrin; Livendahl, Madeleine; Adolfsson, Hans; Tetrahedron Letters; vol. 50; nb. 46; (2009); p. 6321 - 6324 View in Reaxys With potassium tert-butylate, hydrogen in isopropyl alcohol, Time= 15h, T= 20 °C , p= 3800.26Torr , enantioselective reaction Li, Wei; Hou, Guohua; Wang, Chunjiang; Jiang, Yutong; Zhang, Xumu; Chemical Communications; vol. 46; nb. 22; (2010); p. 3979 - 3981 View in Reaxys With formic acid, C28H28ClN2O2RuS, triethylamine, Time= 10h, T= 28 °C , optical yield given as percent ee, enantioselective reaction Martins, Jose E.D.; Contreras Redondo, Miguel A.; Wills, Martin; Tetrahedron Asymmetry; vol. 21; nb. 18; (2010); p. 2258 - 2264 View in Reaxys With C59H71ClFeN2O2OsP2, sodium isopropylate, isopropyl alcohol, Time= 0.5h, T= 60 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Baratta, Walter; Benedetti, Fabio; Del Zotto, Alessandro; Fanfoni, Lidia; Felluga, Fulvia; Magnolia, Santo; Putignano, Elisabetta; Rigo, Pierluigi; Organometallics; vol. 29; nb. 16; (2010); p. 3563 - 3570 View in Reaxys With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer, (S)-tert-butyl 1-((1-benzyl-1H-1,2,3-triazol-4-yl)methylamino)-3-methyl-1-thioxobutan-2-ylcarbamate, sodium isopropylate, isopropyl alcohol, lithium chloride, Time= 2h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Tinnis, Fredrik; Adolfsson, Hans; Organic and Biomolecular Chemistry; vol. 8; nb. 20; (2010); p. 4536 - 4539 View in Reaxys With recombinant stereospecific carbonyl reductase 1 from Candida parapsilosis, NAD in aq. phosphate buffer, Time= 6h, T= 30 °C , pH= 6.5 Nie, Yao; Xiao, Rong; Xu, Yan; Montelione, Gaetano T.; Organic and Biomolecular Chemistry; vol. 9; nb. 11; (2011); p. 4070 - 4078 View in Reaxys With [RhCl2(p-cymene)]2, C2F3O2 (1-)*C2HF3O2*C28H37N4O3S(1+), sodium formate in water, Time= 4h, T= 40 °C , Inert atmosphere, optical yield given as percent ee Zhou, Zhongqiang; Ma, Qiong; Sun, Yong; Zhang, Aiqing; Li, Lin; Heteroatom Chemistry; vol. 21; nb. 7; (2010); p. 505 514 View in Reaxys With formic acid, [RhCl2(p-cymene)]2, C18H24N2O2S, triethylamine, Time= 36h, T= 40 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction

122/258

2018-07-03 17:29:03

Zhang, Bo; Wang, Hui; Lin, Guo-Qiang; Xu, Ming-Hua; European Journal of Organic Chemistry; nb. 22; (2011); p. 4205 4211 View in Reaxys Reaction Steps: 3 1.1: sodium tetrahydroborate / methanol / 0.5 h / 20 °C 1.2: 0.17 h / 20 °C / Saturated solution 2.1: immobilized CALB lipase / 32 h / 30 °C / Enzymatic reaction 3.1: immobilized CALB lipase; ammonia / di-isopropyl ether / 13 h / 35 °C / Enzymatic reaction With sodium tetrahydroborate, immobilized CALB lipase, ammonia in methanol, di-isopropyl ether Wang, Bo; Jiang, Ling; Wang, Jue; Ma, Jingbo; Liu, Min; Yu, Hongwei; Tetrahedron Asymmetry; vol. 22; nb. 9; (2011); p. 980 - 985 View in Reaxys With formic acid, C31H33ClN2O3RuS, triethylamine, Time= 24h, T= 60 °C , Inert atmosphere, enantioselective reaction Touge, Taichiro; Hakamata, Tomohiko; Nara, Hideki; Kobayashi, Tohru; Sayo, Noboru; Saito, Takao; Kayaki, Yoshihito; Ikariya, Takao; Journal of the American Chemical Society; vol. 133; nb. 38; (2011); p. 14960 - 14963 View in Reaxys With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, C2F3O2 (1-)*C2HF3O2*C26H28N5O3S(1+), triethylammonium formate, Time= 23h, T= 40 °C , Inert atmosphere, Ionic liquid, optical yield given as percent ee Zhou, Zhongqiang; Sun, Yong; Zhang, Aiqing; Central European Journal of Chemistry; vol. 9; nb. 1; (2011); p. 175 - 179 View in Reaxys With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer, C25H36N2O7S, sodium isopropylate, lithium chloride in tetrahydrofuran, isopropyl alcohol, Time= 24h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Coll, Mercedes; Ahlford, Katrin; Pamies, Oscar; Adolfsson, Hans; Dieguez, Montserrat; Advanced Synthesis and Catalysis; vol. 354; nb. 2-3; (2012); p. 415 - 427 View in Reaxys 38 :A solution of the ketone in 2-propanol was added to a 50 mL Schlenk flask. After evacuating and refilling with argon, a mixture of the catalyst and base (eg. KO'Bu) was added. The resulting mixture was then injected into a 50 mL autoclave which had been previously placed under an atmosphere of hydrogen. The autoclave was pressurized with hydrogen gas and the reaction mixture was stirred at the desired temperature. The reaction progress was monitored by TLC. Upon completion of the reaction, the solvent was removed under vacuum and the mixture was filtered through a short pad of silica gel (ca. 6 cm) using hexane/ ethyl acetate. The solvent was then removed from the filtrate affording the product. With potassium tert-butylate, hydrogen, RuCl2((S)-Xylyl-Garphos)((S)-DAIPEN) in isopropyl alcohol, Time= 3.5h, T= 25 °C , p= 7600.51Torr , Product distribution / selectivity Patent; KANATA CHEMICAL TECHNOLOGIES INC.; ABDUR-RASHID, Kamaluddin; JIA, Wenli; LU, Shuiming; GUO, Rongwei; CHEN, Xuanhua; AMOROSO, Dino; WO2012/31358; (2012); (A1) English View in Reaxys 15 :<Example 15>Asymmetric hydrogen transfer reaction of propiophneone using a complex RuCl((R,R>0-HT-Tsdpen)In a 15ml Schlenk tube, 3.3 mg (0.005 mmol) of RuCl((R,R)-0-HT-Tsdpen), 0.67 ml (0.67 g, 5.0 mmol) of propiophenone, and 2.5 ml of a formic acid-triethylamine (5:2) azeotropic mixture were mixed, and the Schlenk tube was purged with nitrogen. Subsequently, the mixture was allowed to react for 24 hours at 60°C. An analysis of the reaction liquid was carried out by GC, and it was found that (R)-l-phenylpropan-l-ol with 93.7percent ee was produced at a conversion rate of 99.7percent. With formic acid, triethylamine, (R,R)-Ts-DENEB, Time= 24h, T= 60 °C , Inert atmosphere, Product distribution / selectivity Patent; TAKASAGO INTERNATIONAL CORPORATION; TOUGE, Taichiro; NARA, Hideki; HAKAMADA, Tomohiko; WO2012/26201; (2012); (A1) English View in Reaxys With sodium formate in water, Time= 1h, T= 40 °C , optical yield given as percent ee, enantioselective reaction Tang, Shuang; Jin, Ronghua; Zhang, Huaisheng; Yao, Hui; Zhuang, Jinglan; Liu, Guohua; Li, Hexing; Chemical Communications; vol. 48; nb. 50; (2012); p. 6286 - 6288

123/258

2018-07-03 17:29:03

View in Reaxys With C46H43Cl2FeNOP2Ru, potassium isopropoxide, isopropyl alcohol, Time= 0.166667h, T= 20 °C , optical yield given as percent ee, enantioselective reaction Zirakzadeh, Afrooz; Schuecker, Raffael; Gorgas, Nikolaus; Mereiter, Kurt; Spindler, Felix; Weissensteiner, Walter; Organometallics; vol. 31; nb. 11; (2012); p. 4241 - 4250 View in Reaxys 89 %Spectr. With [ReOCl3((R)-1-[(Sp)-2-(dicyclohexyl)ferrocenyl]ethyldi[3,5-bis(trifluoromethyl)phenyl]phosphane)], triethylamine in isopropyl alcohol, Time= 20h, T= 80 °C , Inert atmosphere, Schlenk technique Mejia, Esteban; Aardoom, Raphael; Togni, Antonio; European Journal of Inorganic Chemistry; nb. 31; (2012); p. 5021 5032,12 View in Reaxys With sodium formate in water, Time= 3h, T= 40 °C , enantioselective reaction Xiao, Wei; Jin, Ronghua; Cheng, Tanyu; Xia, Daquan; Yao, Hui; Gao, Fei; Deng, Boxin; Liu, Guohua; Chemical Communications; vol. 48; nb. 97; (2012); p. 11898 - 11900 View in Reaxys With trans-[OsCl2(P(OPh)3){2,6-bis[4η-(S)-isopropyloxazolin-2η-yl]pyridine}], potassium tert-butylate, isopropyl alcohol, Time= 1h, T= 82 °C , Inert atmosphere, Schlenk technique, Reagent/catalyst, enantioselective reaction Vega, Esmeralda; Lastra; Gamasa, M. Pilar; Inorganic Chemistry; vol. 52; nb. 10; (2013); p. 6193 - 6198 View in Reaxys General procedure for ketone reduction using catalysts 12–18 General procedure: To a ketone (2.4 mmol) placed in a vial, 1 mL of CH3CN solution of preformed ruthenium catalyst (24 lmol) and formic acid/triethylamine azeotropic mixture (1 mL) were added. The mixture was then stirred at room temperature and the progress of the reaction was monitored by TLC until the specified conversion was achieved. After evaporation of the solvents, 4 mL of CH2Cl2 and 1.5 mL of 10percent aqueous HCl solution were added to the residue. The layers were separated and the water layer was extracted twice with 2 mL of CH2Cl2. The combined organic layers were dried over Na2SO4 and the solvent was evaporated in vacuo. The oily residue was purified by column chromatography on silica gel using chloroform (dried over CaCl2) as eluent to afford the appropriate ketone. The enantiomeric excess was determined by GC analysis using a Supelco cyclodextrinb-DEX 120 capillary column (20 m 0.25 mm I.D. and 0.25 lm film thickness). With formic acid, C23H30ClN2O2RuS, triethylamine in acetonitrile, Time= 72h, T= 20 °C Roszkowski, Piotr; Maurin, Jan K.; Czarnocki, Zbigniew; Tetrahedron Asymmetry; vol. 24; nb. 11; (2013); p. 643 - 650 View in Reaxys 4.21 NMR monitoring experiments General procedure: In a NMR tube equipped with a magnetic stirrer were added ruthenium dimer (0.005mmol), diamine ligand (0.01mmol) and d6-benzene (0.05cm3) in the formic acid/ triethylamine (5:2) azeotropic mixture (0.7cm3). The NMR tube was shaken gently and a NMR cap with holes was then fitted. The catalytic mixture was stirred at 28°C for 1h, after which acetophenone (1.1mmol) was added using a syringe. The NMR tube was again shaken gently using a cap without holes and then left to stir at 28°C for the amount of time recorded. The reduction was monitored in two ways: (1) an NMR tube was placed in the NMR spectrometer, and the reaction monitored using a pre-set programme which records chromatograms at regular intervals at 28°C; and (2) at intervals the NMR sample was removed from the oil bath set at 28°C and analysed using the NMR spectrometer. Data analysis was performed using the MestreC software. The conversion of acetophenone to 1-phenylethanol was calculated by comparing the integration of the proton CHOH in the product alcohol (4.9ppm) with the integration of the 3 protons CH3 in acetophenone (2.5ppm). With [(η6-C6H6)Ru(μ-Cl)Cl]2, formic acid, triethylamine, Time= 1h, T= 28 °C , Inert atmosphere, enantioselective reaction Zammit, Charlotte M.; Wills, Martin; Tetrahedron Asymmetry; vol. 24; nb. 13-14; (2013); p. 844 - 852 View in Reaxys With formic acid, N-{(1R,2R)-2-[3-(4-methoxyphenyl)propylamino]-1,2-diphenylethyl}-4-methylbenzenesulfonamide ruthenium chloride, triethylamine, Time= 3.5h, T= 60 °C , Inert atmosphere, Time Soni, Rina; Jolley, Katherine E.; Clarkson, Guy J.; Wills, Martin; Organic Letters; vol. 15; nb. 19; (2013); p. 5110 - 5113

124/258

2018-07-03 17:29:03

View in Reaxys With potassium tert-butylate, hydrogen in isopropyl alcohol, tert-butyl alcohol, Time= 2.5h, T= 20 °C , p= 1875.19 3375.34Torr , enantioselective reaction Chaplin, David; Harrison, Paul; Henschke, Julian P.; Lennon, Ian C.; Meek, Graham; Moran, Paul; Pilkington, Christopher J.; Ramsden, James A.; Watkins, Simon; Zanotti-Gerosa, Antonio; Organic Process Research and Development; vol. 7; nb. 1; (2003); p. 89 - 94 View in Reaxys With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer, C33H44N2O8S, sodium isopropylate, lithium chloride in tetrahydrofuran, isopropyl alcohol, Time= 79h, T= 20 °C , Inert atmosphere, Schlenk technique, enantioselective reaction Coll, Mercedes; Pamies, Oscar; Adolfsson, Hans; Dieguez, Montserrat; ChemCatChem; vol. 5; nb. 12; (2013); p. 3821 3828 View in Reaxys With alcohol dehydrogenase from Lactobacillus brevis, isopropyl alcohol in aq. phosphate buffer, Time= 48h, T= 30 °C , pH= 7.5, Enzymatic reaction, Kinetics, enantioselective reaction Rodriguez, Cristina; Borzecka, Wioleta; Sattler, Johann H.; Kroutil, Wolfgang; Lavandera, Ivan; Gotor, Vicente; Organic and Biomolecular Chemistry; vol. 12; nb. 4; (2014); p. 673 - 681 View in Reaxys Catalyst (0.01 mmol) was placed in a Schlenk tube under an inert atmosphere followed by HCOONa (0.340g, 5.0 mmol) and H20 (1 mL). The mixture was degassed three times and to this solution ketone (lmmol) was added followed by degassing 2 times. The mixture was stirred at 60 °C. The reaction was monitored by chiral GC. For chiral GC analysis, the sample from the reaction mixture was diluted with Et20 and H20. The organic layer was separated, filtered through a short column of silica using hexane: EtOAc (1 : 1). The filtrate was analysed by chiral GC. After completion of the reaction, the reaction mixture was diluted with H20 and extracted with Et20 (2x5 mL). The organic layers were combined, dried over anhy. Na2S04, filtered and concentrated to give crude compound. The crude compound was purified by flash column chromatography to give pure product. With N-{(1R,2R)-2-[3-(4-methoxyphenyl)propylamino]-1,2-diphenylethyl}-4-methylbenzenesulfonamide ruthenium chloride, sodium acetate, Time= 1.5h, T= 60 °C , Inert atmosphere, Schlenk technique, Reagent/catalyst, Time Patent; THE UNIVERSITY OF WARWICK; WILLS, Martin; JOLLEY, Katherine Emma; SONI, Rina; WO2014/68331; (2014); (A1) English View in Reaxys 77 %Chromat.

Screening procedure General procedure: Erlenmeyer flasks (300 ml), each containing 100 ml of the medium consisting of 3 g glucose and 1 g aminobac dissolved in water,were inoculated with a suspension of microorganisms and then incubated for 3–7 days at 25 C on a rotary shaker (190 rpm). After full growth of the culture 20 mg of a substrate dissolved in 1 ml of acetone was added. After 1, 3, 6, 9, 12 h and 1, 3, 6, 9 days of incubation under the above conditions, portions of 5 ml of the transformation mixture were taken out and extracted with CHCl3(3*10 ml). The extracts were dried over MgSO4, concentrated in vacuo, and analyzed by GC. All the experiments were repeatedthree times. With yeast culture of Candida viswanathii KCh 120 in acetone, Time= 216h, T= 25 °C , Microbiological reaction, Reagent/ catalyst, enantioselective reaction Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 2 1: sodium tetrahydroborate / methanol 2: yeast culture of Candida parapsilosis KCh 909 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys With formic acid, N-[(1R,2R)-1,2-diphenyl-2-(3-phenylpropylamino)ethyl]methyl sulfonamide ammonium chloride ruthenium, triethylamine, T= 40 °C , Inert atmosphere, Reagent/catalyst, Temperature

125/258

2018-07-03 17:29:03

Hodgkinson, Roy; Jurk, Vclav; Zanotti-Gerosa, Antonio; Nedden, Hans Günter; Blackaby, Andrew; Clarkson, Guy J.; Wills, Martin; Organometallics; vol. 33; nb. 19; (2014); p. 5517 - 5524 View in Reaxys With formic acid, [OsCl2(η6-p-cymene)(N-p-tosyl-1,2-diphenylethylenediamine)], triethylamine, Time= 24h, T= 20 °C , Inert atmosphere, enantioselective reaction Coverdale, James P. C.; Sanchez-Cano, Carlos; Clarkson, Guy J.; Soni, Rina; Wills, Martin; Sadler, Peter J.; Chemistry A European Journal; vol. 21; nb. 22; (2015); p. 8043 - 8046 View in Reaxys Asymmetric Transfer Hydrogenation; General Procedure (Table 1, Entries 1 and 4–19) A 20 mL vial was charged with a stir bar and complex 4 (10 mg, 8.9 × 10–3 mmol). The substrate (4.43 × 10 mmol) was added and the mixture stirred. If the substrate was a liquid, the mixture was stirred until complex 4 had completely dissolved. i-PrOH (3.61 g) was added and the solution was stirred for 5 min. A stock solution of t-BuOK (20 mg, 0.18 mmol) in i-PrOH (0.98 g) was stirred until all the base had dissolved. This stock solution (0.1 g or 0.4 g, 2 and 8 equiv, respectively) was diluted with iPrOH (1.0 g or 0.7 g, respectively) and added to the reaction vial to activate the precatalyst and start catalysis. Samples (0.1 mL) were taken via syringe and injected into Teflon-sealed GC vials prepared with wet, aerated i-PrOH to quench catalysis. With trans-(S,S)-[Fe(Br)(CO)(Ph2PCH2CH2NHCHPhCHPhN=CHCH2PCy2)][BPh4], potassium tert-butylate, isopropyl alcohol, Time= 1h, T= 28 °C , Inert atmosphere, enantioselective reaction Smith, Samantha A.M.; Morris, Robert H.; Synthesis (Germany); vol. 47; nb. 12; (2015); p. 1775 - 1779; Art.No: SS-2014C0753-ST View in Reaxys With anti-Prelog short-chain dehydrogenase/reductase EbSDR8 from Empedobacter brevis ZJUY-1401, isopropyl alcohol, NADH in aq. phosphate buffer, Time= 4h, T= 35 °C , pH= 7.5, Enzymatic reaction, enantioselective reaction Li, Aipeng; Ye, Lidan; Wu, Hongping; Yang, Xiaohong; Yu, Hongwei; Journal of Molecular Catalysis B: Enzymatic; vol. 122; (2015); p. 179 - 187 View in Reaxys With N-{(1R,2R)-2-[3-(4-methoxyphenyl)propylamino]-1,2-diphenylethyl}-4-methylbenzenesulfonamide ruthenium chloride, sodium formate in water, Time= 1.5h, T= 60 °C , Inert atmosphere, Temperature, enantioselective reaction Soni, Rina; Hall, Thomas H.; Mitchell, Benjamin P.; Owen, Matthew R.; Wills, Martin; Journal of Organic Chemistry; vol. 80; nb. 13; (2015); p. 6784 - 6793 View in Reaxys With Debaryomyceshansenii carbonyl reductase N179S/I214F/S215G, NADPH in aq. phosphate buffer, Time= 2h, T= 30 °C , pH= 6.5, Enzymatic reaction, Reagent/catalyst, stereoselective reaction Xu, Guo-Chao; Shang, Yue-Peng; Yu, Hui-Lei; Xu, Jian-He; Chemical Communications; vol. 51; nb. 86; (2015); p. 15728 15731 View in Reaxys With dichloro[[2-(1-methylethoxy-η-O)phenyl]methylene-η-C](tricyclohexylphosphine)ruthenium, potassium tert-butylate, (R,R)N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine in tetrahydrofuran, isopropyl alcohol, Time= 20h, T= 30 °C , Inert atmosphere, Glovebox, enantioselective reaction Renom-Carrasco, Marc; Gajewski, Piotr; Pignataro, Luca; De Vries, Johannes G.; Piarulli, Umberto; Gennari, Cesare; Lefort, Laurent; Advanced Synthesis and Catalysis; vol. 358; nb. 4; (2016); p. 515 - 519 View in Reaxys 95 %Chromat.

2.3.1. Procedure using [IrCl(cod)]2as an Ir catalyst precursor General procedure: A flask was charged with azolium salt L12 (0.02 mmol, 9.1 mg),Ag2O (0.01 mmol, 2.4 mg) and CH2Cl2(1 mL). After stirring the resulting mixture at room temperature for 2 h in the dark, CH2Cl2 was removed in vacuo. Then, a THF (1 mL) solution of [IrCl(cod)]2(0.01 mmol, 6.9 mg) was added to the reaction vessel. The resulting mixture was stirred at room temperature for an additional 4 h in the dark, filtered through a membrane filter, and evaporated to dry-ness in vacuo. Subsequently, to the resulting flask containing yellow solid of the unpurified IrCl(cod)(NHC) complex, a solution of AgBF4(0.025 mmol, 4.9 mg) in CPME (2 mL) was added, and then stirred at room temperature for 1 h. Finally, propiophenone (0.5 mmol,66 mg) and (EtO)2MeSiH (2.25 mmol, 294 mg) were added to the resulting CPME solution (see Appendix A. Supplementary data fordetails). After stirring at room temperature for 20 h under open-air conditions, K2CO3(2 mg) and MeOH (2 mL) were added. Then, the resulting mixture was stirred at room temperature for 2 h. Afterevaporation of the solvents, the residue obtained was

126/258

2018-07-03 17:29:03

purified bycolumn chromatography on silica gel (Et2O/n-hexane = 3:7) to give(S)-1-phenyl-1-propanol (61 mg, 91percent isolated yield). The ee was measured by chiral GLC. With silver tetrafluoroborate, diethoxymethylane, C26H29N3O2*Cl(1-)*Ir(1+)*C8H12, Time= 20h, T= 20 °C , stereoselective reaction Manabe, Yoshiki; Shinohara, Kanako; Nakamura, Hanako; Teramoto, Hiro; Sakaguchi, Satoshi; Journal of Molecular Catalysis A: Chemical; vol. 421; (2016); p. 138 - 145 View in Reaxys Typical preparative scalereactions using TbSADH best mutant General procedure: A test tube (10 mL)containing LB (4 mL) and kanamycin (50 µg/mL) was inoculated with mutant SZ2074 and incubated 8h (37°C, 220 rpm). The pre-culture was then inoculated intoTB (400 mL) containing kanamycin (50 µg/mL) and allowed to grow at 37°C until O.D.was ca. 0.6. IPTG was then added to a final concentration of 0.2 mM and theculture was grown for 16 h (30°C, 180 rpm). Cells were pelleted bycentrifugation, washed once with pH=7.4 potassium phosphate buffer (100 mM) andthen resuspended in pH=7.4 potassium phosphate buffer (45 mL, 100 mM). Cellswere then transferred to a 50 mL Erlenmeyer flask and 1.4 mg/mL lysozyme (70mg), 6U DNase I (50 µL), NADP+ 100mM (200 µL) were added. Substrate 3a (30 mM) in 10percent isopropanol (5 mL)was then added. Biotransformation was carried out at 30°C, 220rpm. GC controlindicated a 92percent conversion after 4h. The reaction was stopped after 6h when theconversion was 94percent. The organic phase was extracted with ethyl acetate (3x100mL) and crude reaction product was purified using column chromatography. (EA:PE1:4, Rf=0.55) afforded (R)-4a as a colourless liquid (157 mg,yield=75percent). With alcohol dehydrogenase TbSADH from Thermoanaerobacter brockii I86N mutant in aq. phosphate buffer, isopropyl alcohol, T= 30 °C , Enzymatic reaction, Reagent/catalyst, enantioselective reaction Sun, Zhoutong; Li, Guangyue; Ilie, Adriana; Reetz, Manfred T.; Tetrahedron Letters; vol. 57; nb. 32; (2016); p. 3648 - 3651 View in Reaxys With DL-dithiothreitol, Thermoanaerobacter ethanolicus secondary alcohol dehydrogenase, NADPH, zinc(II) chloride in isopropyl alcohol, Time= 24h, T= 50 °C , pH= 8, Enzymatic reaction, Kinetics Nealon, Christopher M.; Welsh, Travis P.; Kim, Chang Sup; Phillips, Robert S.; Archives of Biochemistry and Biophysics; vol. 606; (2016); p. 151 - 156 View in Reaxys With ketoreductase P1-A04, NADPH in aq. phosphate buffer, isopropyl alcohol, Time= 24h, T= 30 °C , pH= 7, Enzymatic reaction, Reagent/catalyst, enantioselective reaction Ríos-Lombardía, Nicolás; Vidal, Cristian; Liardo, Elisa; Morís, Francisco; García-Álvarez, Joaquín; González-Sabín, Javier; Angewandte Chemie - International Edition; vol. 55; nb. 30; (2016); p. 8691 - 8695; Angew. Chem.; vol. 128; nb. 30; (2016); p. 8833 - 8837,5 View in Reaxys 94 %Chromat.

With C51H70FeN4P2 (2+)*2BF4 (1-), sodium t-butanolate in isopropyl alcohol, Time= 1.5h, T= 50 °C , Catalytic behavior, Reagent/catalyst, enantioselective reaction Bigler, Raphael; Huber, Raffael; Stöckli, Marco; Mezzetti, Antonio; ACS Catalysis; vol. 6; nb. 10; (2016); p. 6455 - 6464 View in Reaxys With bis(1,5-cyclooctadiene)diiridium(I) dichloride, C49H64FeNOP, hydrogen, sodium hydroxide in isopropyl alcohol, Time= 8h, T= 25 - 30 °C , p= 15201Torr , Autoclave, enantioselective reaction Yu, Jianfei; Duan, Meng; Wu, Weilong; Qi, Xiaotian; Xue, Peng; Lan, Yu; Dong, Xiu-Qin; Zhang, Xumu; Chemistry - A European Journal; vol. 23; nb. 4; (2017); p. 970 - 975 View in Reaxys With Thermoanaerobacter brockii alcohol dehyrogenase TbSADH-1 (A85G/I86A) variant, Time= 1h, T= 30 °C , Enzymatic reaction, Kinetics, Reagent/catalyst, Time, enantioselective reaction Li, Guangyue; Maria-Solano, Miguel A.; Romero-Rivera, Adrian; Osuna, Sílvia; Reetz, Manfred T.; Chemical Communications; vol. 53; nb. 68; (2017); p. 9454 - 9457 View in Reaxys 9 : Ligand L4 and [Ir (COD) Cl] 2 In Situ Catalytic Simple Ketones 4b-4m Asymmetric Hydrogenation

127/258

2018-07-03 17:29:03

General procedure: In the glove box in an argon atmosphere,Ligand L4(7.9 mg, 0.0105 mmol) and [Ir (COD) Cl] 2(3.4 mg, 0.005 mmol) was added to a 2.5 mL vial,With iPrOH (1.0mL) dissolved after room temperature complex for 1h catalyst solution.The catalyst solution (20 uL, 0.0002 mmol) was added to a 5 mL hydrogenated vial,Then, 1.6 mg of tBuOLi (0.02 mmol) was added successively,The substrate ketone 4b-4m (corresponding to the product 5b-5m in the figure below) (0.23 mL, 2 mmol)2mL isopropanol solvent. The hydrogenated vials were placed in a hydrogenation reactor,Hydrogen replaced three times after filling 20atmH2, at room temperature for 6h. After the reaction is completed, the reaction is carried outThe mixture was passed through a short silica gel column.The NMR conversion rate was determined by high performance liquid chromatography (HPLC) or gas chromatography (GC)The enantioselectivity of the reaction is ee. With bis(1,5-cyclooctadiene)diiridium(I) dichloride, C46H66FeNO2P, hydrogen, lithium tert-butoxide in isopropyl alcohol, Time= 6h, T= 20 °C , p= 15201Torr , enantioselective reaction Patent; Wuhan Kaitelisi Technology Co., Ltd.; Zhang Xumu; Yu Jianfei; (13 pag.); CN106632511; (2017); (A) Chinese View in Reaxys 95 %Chromat.

With C39H31Cl2N4OPRu, potassium isopropoxide, isopropyl alcohol, Time= 0.333333h, T= 28 °C , p= 750.075Torr , Inert atmosphere, enantioselective reaction Chai, Huining; Liu, Tingting; Yu, Zhengkun; Organometallics; vol. 36; nb. 21; (2017); p. 4136 - 4144 View in Reaxys With C43H40BrFeN2OP2 (1+)*C24H20B(1-), potassium tert-butylate, isopropyl alcohol, Time= 1h, T= 28 °C , Catalytic behavior, Reagent/catalyst, enantioselective reaction Smith, Samantha A. M.; Prokopchuk, Demyan E.; Morris, Robert H.; Israel Journal of Chemistry; vol. 57; nb. 12; (2017); p. 1204 - 1215 View in Reaxys

H HO

Rx-ID: 3399328 View in Reaxys 4/176 Yield 97 %

Conditions & References Catalytic enantioselective borane reduction of acetophenone by using (S)-2-(anilinodiphenylmethyl)pyrrolidine ((S)-3): typical procedure General procedure: To a THF (1.25 mL) solution of (S)-2-(anilinodiphenylmethyl)pyrrolidine ((S)-3) (99 mg, 0.30 mmol) was added borane-dimethyl sulfide complex (0.12 mL, 1.3 mmol) at 0 °C, and the mixture was refluxed for 45 min with stirring. After the mixture was cooled to room temperature, acetophenone (0.33 mol dm-3 THF solution, 3.0 mL, 1.0 mmol) was added dropwise via syringe pump over 2 h, and stirring was continued for 2 h at room temperature. Then 1 mol dm-3 aqueous HCl was added at 0 °C, and the reaction mixture was stirred at room temperature for 30 min. The aqueous layer was separated and extracted with ether, and the combined organic layers were washed with 1 mol dm-3 aqueous HCl, water, and brine, successively. The organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The resulting crude product was purified by preparative TLC (chloroform) to give (R)-1-phenylethanol (118 mg, 0.96 mmol, 96percent). The ee was determined to be 94percent by HPLC analysis using a chiral column (Daicel Chiralcel OD-H (25*0.46 cm i.d.)); eluent, 5percent 2-propanol in hexane; flow rate, 0.5 mL/min; tR, 17.5 min for major peak, 21.0 min for minor peak. With dimethylsulfide borane complex, (S)-2-(anilinodiphenylmethyl)pyrrolidine in tetrahydrofuran, Time= 2h, T= 20 °C , enantioselective reaction Hosoda, Naoya; Kamito, Hideaki; Takano, Miki; Takebe, Yoshitaka; Yamaguchi, Yoshitaka; Asami, Masatoshi; Tetrahedron; vol. 69; nb. 6; (2013); p. 1739 - 1746 View in Reaxys

77 %

With formic acid, [RuCl2(hexamethylbenzene)]2, (S)-2-piperidinemethanethiol hydrochloride, triethylamine, Time= 24h, T= 30 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Ito, Masato; Shibata, Yuji; Watanabe, Akira; Ikariya, Takao; Synlett; nb. 10; (2009); p. 1621 - 1626

128/258

2018-07-03 17:29:03

View in Reaxys With sodium tetrahydroborate, isobutyric Acid, 1,2:5,6-di-O-isopropylidene-η-D-glucofuranose in tetrahydrofuran, Time= 72h, T= 25 °C , various carboxylic acids reagents; var. aromatic ketones, Product distribution Hirao, Akira; Nakahama, Seiichi; Mochizuki, Hidenori; Itsuno, Shinichi; Yamazaki, Noboru; Journal of Organic Chemistry; vol. 45; nb. 21; (1980); p. 4231 - 4233 View in Reaxys With sodium tetrahydroborate, isobutyric Acid, 1,2:5,6-di-O-isopropylidene-η-D-glucofuranose in tetrahydrofuran, T= 0 °C , other temperatures, carboxylic acids, hydroxymonosaccharides, reagents ratio, Product distribution Hirao, Akira; Itsuno, Shinichi; Owa, Masaki; Nagami, Satoru; Mochizuki, Hidenori; et al.; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); (1981); p. 900 - 905 View in Reaxys With potassium 9-O-(1,2:5,6-di-O-isopropylidene-η-D-glucofuranosyl)-9-boratabicyclo<3.3.1>nonane in tetrahydrofuran, Time= 16h, T= -78 °C , var. reaction temperatures; other aliphatic, alkyl aromatic ketones, and η-halo esters, Product distribution Brown, Herbert C.; Cho, Byung Tae; Park, Won Suh; Journal of Organic Chemistry; vol. 53; nb. 6; (1988); p. 1231 - 1238 View in Reaxys With (R)-2,2'-bis(ethylamino)-1,1'-binaphthyl - LiAlH4 in tetrahydrofuran, Time= 4h, T= -100 °C , other ketone, Product distribution Kabuto, Kuninobu; Yoshida, Takashi; Yamaguchi, Shozo; Miyano, Sotaro; Hashimoto, Harukichi; Journal of Organic Chemistry; vol. 50; nb. 16; (1985); p. 3013 - 3015 View in Reaxys With (S)-(-)-2-amino-3-methylbutan-1-ol*borane in tetrahydrofuran, Time= 60h, T= 30 °C , influence of reagent, solvent, temp. on e.e., Product distribution Hirao, Akira; Itsuno, Shinichi; Nakahama, Seiichi; Yamazaki, Noboru; Journal of the Chemical Society, Chemical Communications; nb. 7; (1981); p. 315 - 317 View in Reaxys With diisobutylaluminium hydride, (S)-1-methyl-2-<(piperidin-1-yl)-methyl>pyrrolidine, tin(ll) chloride in dichloromethane, T= -100 °C , further temperature and solvent, Product distribution Falorni, Massimo; Lardicci, Luciano; Piroddi, Anna Maria; Giacomelli, Giampaolo; Gazzetta Chimica Italiana; vol. 119; nb. 9; (1989); p. 511 - 512 View in Reaxys With nicotinamide adenine dinucleotide, rat liver homogenate supernatant, T= 37 °C , other catalysts, Product distribution Prelusky; Coutts; Pasutto; Journal of Pharmaceutical Sciences; vol. 71; nb. 12; (1982); p. 1390 - 1393 View in Reaxys With potassium hydroxide, <Ir(cod)(prophos)>, isopropyl alcohol, Time= 15h, T= 82 °C , hydrogen transfer reduction using various chiral catalysts, various optical yields, Product distribution Spogliarich, R.; Kaspar, J.; Graziani, M.; Morandini, F.; Journal of Organometallic Chemistry; vol. 306; (1986); p. 407 - 412 View in Reaxys With sodium tetrahydroborate, malic acid in tetrahydrofuran, Time= 65h, T= 25 °C , other optically active acids, further aromatic ketones, Product distribution Hirao, Akira; Mochizuki, Hidenori; Zoorob, Hanafi H. Ali; Igarashi, Ichiro; Itsuno, Shinichi; et al.; Agricultural and Biological Chemistry; vol. 45; nb. 3; (1981); p. 693 - 698 View in Reaxys With (-)-7-(1-phenylethyl)-4,5-dihydro-3H-dinaphth<2,3-c;2',3'-e>azepine-borane in benzene, T= 0 °C , asymmetric reduction of prochiral arometic ketones by chiral amine-borane complexes, reduction by borane-amine complexes in the presence of chiralamine-BF3 catalyst; enantiomeric excess, Product distribution Periasamy, Mariappan; Kanth, J. V. Bhaskar; Reddy, Ch. Kishan; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); nb. 4; (1995); p. 427 - 430

129/258

2018-07-03 17:29:03

View in Reaxys With borane-THF, (2S,5S)-2-hydroxymethyl-1,4-diaza<4.3.0>bicyclononane, N,N-diethylaniline, multistep; other ketones, other chiral ligands, other amines; product/yield distribution Falorni, Massimo; Collu, Cristina; Giacomelli, Giampaolo; Tetrahedron Asymmetry; vol. 7; nb. 9; (1996); p. 2739 - 2742 View in Reaxys With lithium aluminium tetrahydride, N,N-Bis-<(S)-2-Hydroxy-propyl>-(S)-η-methylbenzylamine, eepercent = 77(R), var. chiral aminodiols, Yield given. Yields of byproduct given. Title compound not separated from byproducts Morrison, James D.; Grandbois, Edward R.; Howard, Sachiko I.; Weisman, Gary R.; Tetrahedron Letters; vol. 22; nb. 28; (1981); p. 2619 - 2622 View in Reaxys With hydrogenchloride, dimethylsulfide borane complex, (S)-oxazaborolidine in tetrahydrofuran, Time= 0.166667h, Ambient temperature, Yield given Youn, In Kwon; Lee, Sang Who; Pak, Chwang Siek; Tetrahedron Letters; vol. 29; nb. 35; (1988); p. 4453 - 4456 View in Reaxys With sodium tetrahydroborate, 1,2:5,6-di-O-isopropylidene-η-D-glucofuranose, isobutyric Acid in tetrahydrofuran, Time= 72h, T= 25 °C , Yield given Hirao, Akira; Nakahama, Seiichi; Mochizuki, Hidenori; Itsuno, Shinichi; Yamazaki, Noboru; Journal of Organic Chemistry; vol. 45; nb. 21; (1980); p. 4231 - 4233 View in Reaxys With methanol, THF·BF3, endo-2-hydroxy-3-(1-methyl-2-pyrrolyl)methylamino-1,7,7-trimethylnorbornane, 1.) THF, RT, 5 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Tanaka, Kazuhiko; Matsui, Junichi; Suzuki, Hitomi; Journal of the Chemical Society, Chemical Communications; nb. 18; (1991); p. 1311 - 1312 View in Reaxys in ethanol, Time= 504h, T= 25 °C , immobilized Gardenia jasminoides cells, Yield given. Yields of byproduct given. Title compound not separated from byproducts Naoshima, Yoshinobu; Akakabe, Yoshihiko; Phytochemistry (Elsevier); vol. 30; nb. 11; (1991); p. 3595 - 3598 View in Reaxys With (2S)-(-)-2-amino-3-methyl-1,1-diphenylbutan-1-ol-borane in tetrahydrofuran, Time= 2h, T= 30 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Itsuno, Shinichi; Nakano, Michio; Miyazaki, Koji; Masuda, Hirofumi; Ito, Koichi; et al.; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); (1985); p. 2039 - 2044 View in Reaxys With (S)-benzylpyrrolidin-2-ylmethanol-borane in tetrahydrofuran, Time= 72h, T= 30 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Itsuno, Shinichi; Ito, Koichi; Hirao, Akira; Nakahama, Seiichi; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); nb. 12; (1984); p. 2887 - 2893 View in Reaxys With potassium 9-O-(1,2:5,6-di-O-isopropylidene-η-D-glucofuranosyl)-9-boratabicyclo<3.3.1>nonane in tetrahydrofuran, Time= 16h, T= -78 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Brown, Herbert C.; Cho, Byung Tae; Park, Won Suh; Journal of Organic Chemistry; vol. 53; nb. 6; (1988); p. 1231 - 1238 View in Reaxys With lithium aluminium tetrahydride, (R)-2,2'-dimethoxy-6,6'-dimethylbiphenyl, 1) THF, -10 to 20 deg C 2) THF, -100 deg C, 4 h, then -78 deg C, 16 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Suda, Hiroshi; Kanoh, Shigeyoshi; Umeda, Nobuhiro; Ikka, Masahiko; Motoi, Masatoshi; Chemistry Letters; (1984); p. 899 - 902

130/258

2018-07-03 17:29:03

View in Reaxys With diisobutylaluminium hydride, (S)-1-methyl-2-<(piperidin-1-yl)-methyl>pyrrolidine, tin(ll) chloride in dichloromethane, Time= 0.166667h, T= -100 °C , Yield given. Yields of byproduct given Oriyama, Takeshi; Mukaiyama, Teruaki; Chemistry Letters; (1984); p. 2071 - 2074 View in Reaxys With reagent prepared form (1S,2S)-(+)-2-amino-3-methoxy-1-phenyl-1-propanol and borane-methyl sulfide in tetrahydrofuran, 1.) 0 deg C -> 25 deg C, 2.) 25 deg C, 2 h, Yield given. Yields of byproduct given. Title compound not separated from byproducts Mandal, Arun K.; Kasar, T. G.; Mahajan, S. W.; Jawalkar, D. G.; Synthetic Communications; vol. 17; nb. 5; (1987); p. 563 574 View in Reaxys With borane-THF, (4S,5R)-3,4-dimethyl-5-phenyl-1,3,2-oxazaborolidine in tetrahydrofuran, Time= 0.166667h, T= 0 °C , Title compound not separated from byproducts Cho, Buyng Tae; Chun, Yu Sung; Tetrahedron: Asymmetry; vol. 3; nb. 12; (1992); p. 1539 - 1542 View in Reaxys With (S)-tetrahydro-1-methyl-3,3-diphenyl-1H,3H-pyrrolo[1,2-c]-[1,3,2]-oxazaborole-borane in dichloromethane, T= -20 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Mathre, David J.; Thompson, Andrew S.; Douglas, Alan W.; Hoogsteen, Karst; Caroll, James D.; et al.; Journal of Organic Chemistry; vol. 58; nb. 10; (1993); p. 2880 - 2888 View in Reaxys With borane-THF, chiral oxazaborolidine in tetrahydrofuran, Time= 0.0833333h, T= 30 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Nakagawa; Kawate; Kakikawa; Yamada; Matsui; Hino; Tetrahedron; vol. 49; nb. 9; (1993); p. 1739 - 1748 View in Reaxys With (S)-oxazaborolidine, borane in tetrahydrofuran, Time= 0.166667h, T= 25 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Kim, Yong Hae; Park, Doo Han; Byun, Il Suk; Yoon, I. K.; Park, C. S.; Journal of Organic Chemistry; vol. 58; nb. 17; (1993); p. 4511 - 4512 View in Reaxys With borane-THF, (S)-η,η-diphenyl-(indolin-2-yl)methanol in tetrahydrofuran, T= 30 °C , Title compound not separated from byproducts Martens, Juergen; Dauelsberg, Ch.; Behnen, W.; Wallbaum, S.; Tetrahedron: Asymmetry; vol. 3; nb. 3; (1992); p. 347 - 350 View in Reaxys With 9-O-(1,2-isopropylidene-5-deoxy-η-D-xylofuranosyl)-9-boratabicyclo<3.3.1>nonane potassium in tetrahydrofuran, Time= 30h, T= -78 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Cho, Byung Tae; Chun, Yu Sung; Tetrahedron: Asymmetry; vol. 3; nb. 1; (1992); p. 73 - 84 View in Reaxys With lithium aluminium tetrahydride, (2R,3R)-4-dimethylamino-3-methyl-1,2-diphenyl-butan-2-ol, 1) diethyl ether, -78 deg C, 4 min, 2) diethyl ether, a) -78 deg C, 1 h, b) 12 h, room temp., Yield given. Multistep reaction. Title compound not separated from byproducts Zadel, Guido; Rieger, Rainer; Breitmaier, Eberhard; Liebigs Annalen der Chemie; nb. 12; (1991); p. 1343 - 1346 View in Reaxys With sodium tetrahydroborate, chloro-trimethyl-silane, (S)-1,1-diphenyl-2-(S-phenylsulfonimidoyl)ethanol in tetrahydrofuran, Time= 3h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Bolm, Carsten; Seger, Andreas; Felder, Marcel; Tetrahedron Letters; vol. 34; nb. 50; (1993); p. 8079 - 8080 View in Reaxys

131/258

2018-07-03 17:29:03

With diphenylsilane, toluene-4-sulfonic acid, chloro(1,5-cyclooctadiene)rhodium(I) dimer, phosphonite 3a, 1.) PhH, 0 deg C up to RT, overnight; 2.) MeOH, RT, 5 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Sakaki, Jun-ichi; Schweizer, W. Bernd; Seebach, Dieter; Helvetica Chimica Acta; vol. 76; (1993); p. 2654 - 2665 View in Reaxys With dimethylsulfide borane complex, (S)-Ph(NH)S(O)CH2C(Ph)2OH in toluene, Time= 3h, Ambient temperature, Yield given. Title compound not separated from byproducts Bolm; Felder; Tetrahedron Letters; vol. 34; nb. 38; (1993); p. 6041 - 6044 View in Reaxys With chiral (R,R)-<(R)-styrene oxide/benzylamine/samarium(III)>, isopropyl alcohol, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Evans, David A.; Nelson, Scott G.; Gagne, Michel R.; Muci, Alexander R.; Journal of the American Chemical Society; vol. 115; nb. 21; (1993); p. 9800 - 9801 View in Reaxys With potassium hydroxide, N-acetyl-(S)-methionine (R,S)-sulphoxide, isopropyl alcohol, <RhCl(hd)2>, Time= 10h, Heating, Title compound not separated from byproducts Kvintovics, Pal; James, Brian R.; Heil, Balint; Journal of the Chemical Society, Chemical Communications; nb. 24; (1986); p. 1810 - 1811 View in Reaxys With lithium borohydride, N,N'-bis(benzoyl)-D-cystine, tert-butyl alcohol in tetrahydrofuran, T= -78 - -30 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Soai, Kenso; Oyamada, Hidekazu; Yamanoi, Takashi; Journal of the Chemical Society, Chemical Communications; nb. 7; (1984); p. 413 - 414 View in Reaxys With borane, 1,1-diphenyl-L-valinol in tetrahydrofuran, Time= 2h, T= 30 °C , Title compound not separated from byproducts Itsuno, Shinichi; Ito, Koichi; Hirao, Akira; Nakahama, Seiichi; Journal of the Chemical Society, Chemical Communications; nb. 8; (1983); p. 469 - 470 View in Reaxys With Chirald-<ZnCRA*> in tetrahydrofuran, Time= 17h, T= 25 °C , Yield given. Yields of byproduct given Feghouli, Abdelhafid; Vanderesse, Regis; Fort, Yves; Caubere, Paul; Journal of the Chemical Society, Chemical Communications; (1989); p. 224 - 225 View in Reaxys With borane-THF, Trimethylboroxine, (1S,2R)-1-amino-2-indanol in tetrahydrofuran, toluene, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Hong, Yaping; Gao, Yun; Nie, Xiaoyi; Zepp, Charles M.; Tetrahedron Letters; vol. 35; nb. 36; (1994); p. 6631 - 6634 View in Reaxys With isopropyl alcohol, potassium hydroxide, tetrafluoroboric acid, [Ir(η4-COD)(acac)], (-)-dimenthylphenylphosphine, Time= 34h, T= 83 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Krause, H.W.; Bhatnagar, A.K.; Journal of Organometallic Chemistry; vol. 302; nb. 2; (1986); p. 265 - 268 View in Reaxys With (4S,5R)-4,5-diphenyl-1,3,2-oxazaborolidine, T= 45 - 50 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Yaozhong, Jiang; Yong, Qin; Aiqiao, Mi; Zhitang, Huang; Tetrahedron: Asymmetry; vol. 5; nb. 7; (1994); p. 1211 - 1214 View in Reaxys With lithium aluminium tetrahydride, bis<(1R)-1-hydroxy-1-phenylbutan-2-yl>amine in tetrahydrofuran, Time= 6h, T= -100 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts

132/258

2018-07-03 17:29:03

Vries, Erik F.J. de; Brussee, Johannes; Kruse, Chris G.; Gen, Arne van der; Tetrahedron: Asymmetry; vol. 5; nb. 3; (1994); p. 377 - 386 View in Reaxys With potassium hydroxide, (R)-templated polymerized Rh in isopropyl alcohol, Time= 216h, T= 25 °C , Yield given. Yields of byproduct given Gamez, Patrick; Dunjic, Branko; Pinel, Catherine; Lemaire, Marc; Tetrahedron Letters; vol. 36; nb. 48; (1995); p. 8779 8782 View in Reaxys With borane, (s)-2-amino-1,1-diphenyl-3-(2-naphthyl)-1-propanol in tetrahydrofuran, Time= 3h, T= 30 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Zhang; Shen; Liu; Chen; Synthetic Communications; vol. 25; nb. 21; (1995); p. 3407 - 3411 View in Reaxys With sodium hydroxide, isopropyl alcohol, <RuCl2(NCH(iPr)CH2OCH-o-DBP-C6H5)(PPh3)>, Time= 0.166667h, T= 82 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Langer; Helmchen; Tetrahedron Letters; vol. 37; nb. 9; (1996); p. 1381 - 1384 View in Reaxys With borane-THF, (+)-1-(1,2,3,4-tetrahydroisoquinoline-1-yl)-cyclopentanol in tetrahydrofuran, Time= 3h, T= 30 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Reiners; Martens; Tetrahedron Asymmetry; vol. 8; nb. 2; (1997); p. 277 - 281 View in Reaxys With borane, (S)-2-amino-3-(2,5-dimethylphenyl)-1,1-diphenyl-1-propanol in tetrahydrofuran, Time= 0.75h, T= 30 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Zhang, Ya-Wen; Shen, Zong-Xuan; Gu, De-Ben; Chen, Wei-Yi; Fei, Zheng-Hao; Dai, Qing-Fei; Synthetic Communications; vol. 26; nb. 23; (1996); p. 4415 - 4420 View in Reaxys With dimethylsulfide borane complex, (2S,4R)-η,η-diphenyl-2-<(4-allyloxy)-N-benzyloxycarbonyl>pyrrolidinemethanol and methyl hydrosiloxane-dimethylsiloxane copolymer in tetrahydrofuran, Time= 0.5h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Felder, Marcel; Giffels, Guido; Wandrey, Christian; Tetrahedron Asymmetry; vol. 8; nb. 12; (1997); p. 1975 - 1977 View in Reaxys With borane, (S)-2-amino-3-(2-chlorophenyl)-1,1-diphenyl-1-propanol in tetrahydrofuran, Yield given. Yields of byproduct given. Title compound not separated from byproducts Shen, Zong-Xuan; Lu, Jun; Zhang, Qing; Zhang, Ya-Wen; Tetrahedron Asymmetry; vol. 8; nb. 14; (1997); p. 2287 - 2289 View in Reaxys With 1,1,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy]trisiloxane, chiral ammonium fluoride salt 3a in tetrahydrofuran, Ambient temperature, Yield given. Yields of byproduct given Drew, Mark D.; Lawrence, Nicholas J.; Watson, William; Bowles, Stephen A.; Tetrahedron Letters; vol. 38; nb. 33; (1997); p. 5857 - 5860 View in Reaxys With chloro(1,5-cyclooctadiene)rhodium(I) dimer, (+)-2-<2-(diphenylphosphino)phenyl>oxazoline derived from cis-2-amino-3,3-dimethyl-1-indanol, diphenylsilane in toluene, Time= 24h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Sudo, Atsushi; Yoshida, Hiroaki; Saigo, Kazuhiko; Tetrahedron Asymmetry; vol. 8; nb. 19; (1997); p. 3205 - 3208 View in Reaxys With dimethylsulfide borane complex, η,η-diphenyltyrosinol in tetrahydrofuran, Time= 24h, T= 20 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Giffels, Guido; Beliczey, Juliane; Felder, Marcel; Kragl, Udo; Tetrahedron Asymmetry; vol. 9; nb. 4; (1998); p. 691 - 696

133/258

2018-07-03 17:29:03

View in Reaxys With IrCl(cod)2, chiral 2-benzyl-1,1-di(p-anisyl)ethylenediamine in isopropyl alcohol, Time= 12h, Ambient temperature, Yield given. Yields of byproduct given Inoue, Shin-Ichi; Nomura, Kenji; Hashiguchi, Shohei; Noyori, Ryoji; Izawa, Yasuji; Chemistry Letters; nb. 9; (1997); p. 957 - 958 View in Reaxys With potassium hydroxide, [(η6-p-Cymene)2Ru(Cl)2], L-proline in isopropyl alcohol, Time= 24h, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Ohta, Tetsuo; Nakahara, Shu-Ichi; Shigemura, Yasuhiko; Hattori, Kouichi; Furukawa, Isao; Chemistry Letters; nb. 6; (1998); p. 491 - 492 View in Reaxys With complex of LAH in tetrahydrofuran, Time= 9h, T= -78 °C , Title compound not separated from byproducts Malkar; Kumar; Synthetic Communications; vol. 28; nb. 23; (1998); p. 4445 - 4461 View in Reaxys With dimethylsulfide borane complex, (S)-(-)-2-butyl-CBS-oxazaborolidine in toluene, Time= 0.5h, T= -10 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Manju, Kavita; Trehan, Sanjay; Tetrahedron Asymmetry; vol. 9; nb. 19; (1998); p. 3365 - 3369 View in Reaxys With methanol, THF·BF3, exo-2-hydroxy-3-(1-methyl-2-pyrrolyl)methylamino-1,7,7-trimethylnorbornane, 1.) THF, RT, 5 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Tanaka, Kazuhiko; Matsui, Junichi; Suzuki, Hitomi; Journal of the Chemical Society, Chemical Communications; nb. 18; (1991); p. 1311 - 1312 View in Reaxys in ethanol, Time= 264h, T= 25 °C , immobilized Daucus carota cells, Yield given. Yields of byproduct given. Title compound not separated from byproducts Naoshima, Yoshinobu; Akakabe, Yoshihiko; Phytochemistry (Elsevier); vol. 30; nb. 11; (1991); p. 3595 - 3598 View in Reaxys With lithium aluminium tetrahydride, (-)-N-methylephedrine, N-ethylaniline in diethyl ether, Time= 3h, T= -78 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Terashima, Shiro; Tanno, Norihiko; Koga, Kenji; Chemistry Letters; (1980); p. 981 - 984 View in Reaxys With lithium aluminium tetrahydride, (-)-(S)-4-anilino-3-methylaminobutan-1-ol, 1.) THF, room temperature, 1 h; 2.) -100 deg C, 3 h, Yield given. Multistep reaction Sato, Toshio; Goto, Yoshihiko; Fujisawa, Tamotsu; Tetrahedron Letters; vol. 23; nb. 40; (1982); p. 4111 - 4112 View in Reaxys With hydrogenchloride, lithium aluminium tetrahydride, (S)-2-(2,6-xylidinomethyl)pyrrolidine in diethyl ether, Time= 3h, T= -100 °C , Yield given. Yields of byproduct given Mukaiyama, Teruaki; Tetrahedron; vol. 37; nb. 23; (1981); p. 4111 - 4119 View in Reaxys With lithium aluminium tetrahydride, (R)-N2,N2'-diethyl-[1,1'-binaphthyl]-2,2'-diamine, 1.) THF, 60 deg C, 40 min, 2.) THF, -100 deg C, 40 min, Multistep reaction. Title compound not separated from byproducts Kabuto, Kuninobu; Yoshida, Takashi; Yamaguchi, Shozo; Miyano, Sotaro; Hashimoto, Harukichi; Journal of Organic Chemistry; vol. 50; nb. 16; (1985); p. 3013 - 3015 View in Reaxys With 2,2'-iminobis[ethanol], (-)-diisopinocamphenylborane chloride, 1) THF, -25 deg C, 5 h; 2) ethyl ether, 2 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts

134/258

2018-07-03 17:29:03

Brown, Herbert C.; Chandrasekharan, J.; Ramachandran, P. V.; Journal of the American Chemical Society; vol. 110; nb. 5; (1988); p. 1539 - 1546 View in Reaxys With sodium tetrahydroborate, zinc(II) chloride, 1,2:5,6-di-O-isopropylidene-η-D-glucofuranose in tetrahydrofuran, Time= 3h, T= 30 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Hirao, Akira; Ohwa, Masaki; Itsuno, Shinichi; Mochizuki, Hidenori; Nakahara, Seiichi; Yamazaki, Noboru; Bulletin of the Chemical Society of Japan; vol. 54; nb. 5; (1981); p. 1424 - 1428 View in Reaxys With lithium aluminium tetrahydride, (2R,3R)-4-dimethylamino-3-methyl-1,2-diphenyl-butan-2-ol, 1) diethyl ether, a) 20 min, room temp., 2) 10 min, reflux, 2) diethyl ether, 24 h, room temp., Yield given. Multistep reaction. Title compound not separated from byproducts Zadel, Guido; Rieger, Rainer; Breitmaier, Eberhard; Liebigs Annalen der Chemie; nb. 12; (1991); p. 1343 - 1346 View in Reaxys With borane-THF, (R)-1-(η-aminobenzyl)-1-cyclopentanol in tetrahydrofuran, Time= 2h, T= 30 °C , Title compound not separated from byproducts Dauelsberg; Martens; Synthetic Communications; vol. 23; nb. 15; (1993); p. 2091 - 2099 View in Reaxys With n-butyllithium, polymethylhydrosiloxane, chiral titanocene 1,1'-binaphth-2,2'-diolate, tetrabutyl ammonium fluoride, 1.) benzene, hexane, 1 d, 2.) benzene, hexane, THF, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Carter, Mary Beth; Schiott, Birgit; Gutierrez, Alberto; Buchwald, Stephen L.; Journal of the American Chemical Society; vol. 116; nb. 26; (1994); p. 11667 - 11670 View in Reaxys With dimethylsulfide borane complex, (1R)-amino-(2S)-indanol in tetrahydrofuran, Time= 1h, Yield given. Yields of byproduct given. Title compound not separated from byproducts Simone, Bruno Di; Savoia, Diego; Tagliavini, Emilio; Umani-Ronchi, Achille; Tetrahedron: Asymmetry; vol. 6; nb. 1; (1995); p. 301 - 306 View in Reaxys With borane-THF, (1S,2R)-2-amino-1-acenaphthenol in tetrahydrofuran, Time= 0.333333h, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Sudo, Atsushi; Matsumoto, Masaru; Hashimoto, Yukihiko; Saigo, Kazuhiko; Tetrahedron: Asymmetry; vol. 6; nb. 8; (1995); p. 1853 - 1856 View in Reaxys With hydrogenchloride, RhCl(NBD)2, chiral ferrocenylphosphine-imine ligand, diphenylsilane, 1.) THF, 20 deg C, 1 h, 2.) methanol, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Hayashi; Uozumi; Tetrahedron Asymmetry; vol. 6; nb. 10; (1995); p. 2503 - 2506 View in Reaxys With potassium hydroxide, isopropyl alcohol, catalyst prepared from <<RuCl2(η6-C6Me6>2> and (1S,2S)-2-methylamino-1,2diphenylethanol, Time= 2h, T= 28 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Takehara, Jun; Hashiguchi, Shohei; Fujii, Akio; Inoue, Shin-Ichi; Ikariya, Takao; Noyori, Ryoji; Chemical Communications; nb. 2; (1996); p. 233 - 234 View in Reaxys With borane-THF, (1R,2S)-N-(O,O-dimethylphosphoryl)thiolephedrine, Time= 0.5h, T= -20 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Hulst, Ron; Heres, Hero; Peper, Nathalie C.M.W.; Kellogg, Richard M.; Tetrahedron Asymmetry; vol. 7; nb. 5; (1996); p. 1373 - 1384 View in Reaxys

135/258

2018-07-03 17:29:03

With borane-THF, (2S,5S)-2-hydroxymethyl-1,4-diaza<4.3.0>bicyclononane, N,N-diethylaniline, 1.) benzene, reflux, 4 h, 2.) benzene, 20 deg, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Falorni, Massimo; Collu, Cristina; Giacomelli, Giampaolo; Tetrahedron Asymmetry; vol. 7; nb. 9; (1996); p. 2739 - 2742 View in Reaxys With [(η6-C6H6)Ru(μ-Cl)Cl]2, potassium tert-butylate, (R,R)-(PhNHCSNMeCHPh)2 in isopropyl alcohol, Time= 17h, T= 82 °C , Yield given. Yields of byproduct given Touchard, Francois; Gamez, Patrick; Fache, Fabienne; Lemaire, Marc; Tetrahedron Letters; vol. 38; nb. 13; (1997); p. 2275 - 2278 View in Reaxys With lithium aluminium tetrahydride, ethanol, (R,R)-TADDOL, 1.) THF, from -82 deg C to RT, 4 h, 2.) 128 deg C, 14 torr, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Seebach, Dieter; Beck, Albert K.; Dahinden, Robert; Hoffmann, Matthias; Kuehnle, Florian N. M.; Croatica Chemica Acta; vol. 69; nb. 2; (1996); p. 459 - 484 View in Reaxys With [(η6-C6H6)Ru(μ-Cl)Cl]2, (R,R)-(-)-N,N'-dimethyl-1,2-diphenyl-1,2-ethylenyl-diphenyldithiourea, potassium tert-butylate in isopropyl alcohol, Time= 17h, T= 82 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Touchard, Francois; Fache, Fabienne; Lemaire, Marc; Tetrahedron Asymmetry; vol. 8; nb. 19; (1997); p. 3319 - 3326 View in Reaxys With potassium hydroxide, [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, (1R,2S)-1-Amino-2-indanol in isopropyl alcohol, 1.) 80 deg C, 20 min, 80 deg C to rt, 2.) rt, 1.5 h, Yield given. Yields of byproduct given. Title compound not separated from byproducts Palmer; Walsgrove; Wills; Journal of Organic Chemistry; vol. 62; nb. 15; (1997); p. 5226 - 5228 View in Reaxys With (+)-cis-2-amino-1-acenaphthenol, borane in tetrahydrofuran, Yield given. Yields of byproduct given. Title compound not separated from byproducts Saigo; Hashimoto; Sudo; Russian Journal of Organic Chemistry; vol. 32; nb. 2; (1996); p. 230 - 240 View in Reaxys With borane-THF, (R)-2-amino-3-(1-naphthyl)-1,1-diphenyl-1-propanol in tetrahydrofuran, T= 30 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Shen, Zongxuan; Huang, Wei; Feng, Jianwen; Zhang, Yawen; Tetrahedron Asymmetry; vol. 9; nb. 7; (1998); p. 1091 - 1095 View in Reaxys With hydrogen, chiral rhodium bisphosphane in methanol, Time= 40h, T= 25 °C , p= 56254.5Torr , Yield given. Yields of byproduct given. Title compound not separated from byproducts Nagel, Ulrich; Roller, Christoph; Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences; vol. 53; nb. 3; (1998); p. 267 - 270 View in Reaxys With Trimethyl borate, dimethylsulfide borane complex, (1S,3R,4R)-2-azabicyclo<2.2.1>heptane-3-bis(2-naphthyl)methanol in tetrahydrofuran, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Pinho, Pedro; Guijarro, David; Andersson, Pher G.; Tetrahedron; vol. 54; nb. 27; (1998); p. 7897 - 7906 View in Reaxys With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, potassium isopropoxide, isopropyl alcohol, (1S,3R,4R)-3-(hydroxymethyl)-2-azabicyclo<2.2.1>heptane, Time= 1.5h, Ambient temperature, other reagent: 2-propanol/ <RuCl2(hexamethylbenzene)>2/(1S,3R,4R)-3-(hydroxymethyl)-2-azabicyclo<2.2.1>heptane/i-PrOK, Yield given. Yields of byproduct given. Title compound not separated from byproducts Alonso, Diego A.; Guijarro, David; Pinho, Pedro; Temme, Oliver; Andersson, Pher G.; Journal of Organic Chemistry; vol. 63; nb. 8; (1998); p. 2749 - 2751

136/258

2018-07-03 17:29:03

View in Reaxys With dimethylsulfide borane complex, N-(di-p-anisylphosphoryl)-(S)-η,η-diphenyl-2-pyrrolidinemethanol in toluene, T= 110 °C , Reduction, Title compound not separated from byproducts Gamble, Mark P.; Smith, Athene R. C.; Wills, Martin; Journal of Organic Chemistry; vol. 63; nb. 17; (1998); p. 6068 - 6071 View in Reaxys With sodium hydroxide, isopropyl alcohol, tris(triphenylphosphine)ruthenium(II) chloride, chiral oxazolinylferrocenylphosphine, Time= 1h, Heating, Yield given, Yields of byproduct given. Title compound not separated from byproducts Arikawa, Yasuyoshi; Ueoka, Masanao; Matoba, Kazutaka; Nishibayashi, Yoshiaki; Hidai, Masanobu; Uemura, Sakae; Journal of Organometallic Chemistry; vol. 572; nb. 2; (1999); p. 163 - 168 View in Reaxys With 2,6-dimethylpyridine, hydrogen, potassium bromide, chloro(1,5-cyclooctadiene)rhodium(I) dimer, imethyl-7-phosphabicyclo<2.2.1>heptane>, P,P'-1,2-phenylenebis<(1R,2S,4R,5S)-2,5-d in methanol, Time= 88h, T= 20 °C , p= 22800Torr , Yield given, Yields of byproduct given. Title compound not separated from byproducts Jiang, Qiongzhong; Jiang, Yutong; Xiao, Dengming; Cao, Ping; Zhang, Xumu; Angewandte Chemie - International Edition; vol. 37; nb. 8; (1998); p. 1100 - 1103 View in Reaxys With hydrogenchloride, Rh-(R,R)-t-Bu-MiniPHOS, 1-naphthylphenylsilane, 1.) THF, -20 deg C, 2.) H2O, Yield given, Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Yamanoi, Yoshinori; Imamoto, Tsuneo; Journal of Organic Chemistry; vol. 64; nb. 9; (1999); p. 2988 - 2989 View in Reaxys With lithium tetrahydridogallate, R(a)-2-hydroxy-2'-mercapto-1,1'-binaphthyl, benzo[1,3,2]dioxaborole in tetrahydrofuran, diethyl ether, T= -20 °C , Yield given, Yields of byproduct given. Title compound not separated from byproducts Ford, Alan; Woodward, Simon; Angewandte Chemie - International Edition; vol. 38; nb. 3; (1999); p. 335 - 336 View in Reaxys With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate, (S,S)-2,2"-bis<(diethylphosphino)methyl>-1,1"-biferrocene, potassium carbonate, bis(3-fluorophenyl)silane, 1.) -40 deg C, THF, 24 h; 2.) 4 h, r.t., MeOH, Yield given, Multistep reaction. Yields of byproduct given Kuwano; Uemura; Saitoh; Ito; Tetrahedron Letters; vol. 40; nb. 7; (1999); p. 1327 - 1330 View in Reaxys With ruthenium(II) chloride, potassium hydroxide, (R,R)-1,2-diphenylethylenediamine, hydrogen, (2R,2'R)-bis<di(phenyl)phosphino>-(1R,1'R)-dicyclopentane in isopropyl alcohol, Time= 24h, p= 3102.89Torr , Ambient temperature, Yield given, Yields of byproduct given. Title compound not separated from byproducts Cao, Ping; Zhang, Xumu; Journal of Organic Chemistry; vol. 64; nb. 6; (1999); p. 2127 - 2129 View in Reaxys With (1S,2R)-1-(hydroxymethyl)-2-amino-7,7-dimethyl-bicyclo<2.2.1>heptane borane in tetrahydrofuran, Time= 1h, T= 50 °C , Yield given, Yields of byproduct given. Title compound not separated from byproducts Li, Xingshu; Yeung, Chi-Hung; Chan, Albert S. C.; Yang, Teng-Kuei; Tetrahedron Asymmetry; vol. 10; nb. 4; (1999); p. 759 - 763 View in Reaxys With dimethylsulfide borane complex, (2'S)-2,6-bis<(1-methoxycarbonyl-3-thiomethyl)propylaminocarbonyl>pyridine N-oxide in tetrahydrofuran, Time= 0.0833333h, Heating, various chiral pyridine N-oxide ligands, Product distribution Derdau, Volker; Laschat, Sabine; Hupe, Eike; Koenig, Wilfried A.; Dix, Ina; Jones, Peter G.; European Journal of Inorganic Chemistry; nb. 6; (1999); p. 1001 - 1007 View in Reaxys With dimethylsulfide borane complex, N-(8-quinolinyl)sulfonyl-2(S)-(diphenylhydroxymethyl)proline in toluene, Time= 1h, Heating, Reduction, Title compound not separated from byproducts

137/258

2018-07-03 17:29:03

Yang, Gao-Shen; Hu, Jian-Bing; Zhao, Gang; Ding, Yu; Tang, Min-Hua; Tetrahedron Asymmetry; vol. 10; nb. 22; (1999); p. 4307 - 4311 View in Reaxys With dimethylsulfide borane complex, (S)-dendritic chiral amino alcohol in tetrahydrofuran, T= 20 °C , Reduction, Title compound not separated from byproducts Bolm, Carsten; Derrien, Nadine; Seger, Andreas; Chemical Communications; nb. 20; (1999); p. 2087 - 2088 View in Reaxys With dimethylsulfide borane complex, (4R,5R)-2-methyl-4-phenyl-5-methoxymethyl-1,3,2-oxazaborolidine in tetrahydrofuran, toluene, Time= 0.166667h, T= 0 °C , Reduction, Title compound not separated from byproducts Puigjaner, Cristina; Vidal-Ferran, Anton; Moyano, Albert; Pericas, Miquel A.; Riera, Antoni; Journal of Organic Chemistry; vol. 64; nb. 21; (1999); p. 7902 - 7911 View in Reaxys With Zn(C2H5)2[(S,S)-N,N'-ethylene-bis-(1-phenylethylamine)], polymethylhydrosiloxane, sodium bis(2-methoxyethoxy)aluminium dihydride in toluene, Ambient temperature, Title compound not separated from byproducts Mimoun, Hubert; De Saint Laumer, Jean Yves; Giannini, Luca; Scopelliti, Rosario; Floriani, Carlo; Journal of the American Chemical Society; vol. 121; nb. 26; (1999); p. 6158 - 6166 View in Reaxys With dimethylsulfide borane complex, (S)-chiral amino alcohol, aluminum ethoxide in tetrahydrofuran, T= 20 °C , Reduction Yanagi, Takashi; Kikuchi, Ken; Takeuchi, Hideki; Ishikawa, Takehiro; Nishimura, Toshihiro; Kamijo, Tetsuhide; Chemistry Letters; nb. 11; (1999); p. 1203 - 1204 View in Reaxys With potassium isopropoxide, isopropyl alcohol, [Rh(R,R-cycloC6P2N2H4][PF6] in isopropyl alcohol, Time= 22h, T= 82 °C , Catalytic hydrogenation, Title compound not separated from byproducts Gao, Jing-Xing; Yi, Xiao-Dong; Xu, Pian-Pian; Tang, Chun-Liang; Wan, Hui-Lin; Ikariya, Takao; Journal of Organometallic Chemistry; vol. 592; nb. 2; (1999); p. 290 - 295 View in Reaxys With potassium tert-butylate, [RuCl{p-cymene}{NH-benzyl-(1R,2S)-norephedrine}]Cl in isopropyl alcohol, Time= 2h, T= 20 °C , Reduction, Title compound not separated from byproducts Petra, Danielle G. I.; Kamer, Paul C. J.; Van Leeuwen, Piet W. N. M.; Goubitz, Kees; Van Loon, Arjen M.; De Vries, Johannes G.; Schoemaker, Hans E.; European Journal of Inorganic Chemistry; nb. 12; (1999); p. 2335 - 2341 View in Reaxys With (1R,2S)-2-amino-1-phenyl-1-benzylthio-propane, bis(1,5-cyclooctadiene)diiridium(I) dichloride in formic acid, triethylamine, Time= 1h, T= 60 °C , Reduction, Title compound not separated from byproducts Petra, Danielle G. I.; Kamer, Paul C. J.; Spek, Anthony L.; Schoemaker, Hans E.; Van Leeuwen, Piet W. N. M.; Journal of Organic Chemistry; vol. 65; nb. 10; (2000); p. 3010 - 3017 View in Reaxys With potassium tert-butylate, (1S,2R)-2-amino-1,2-diphenyl-1-benzylthio-ethane, bis(1,5-cyclooctadiene)diiridium(I) dichloride in isopropyl alcohol, Time= 1h, T= 20 °C , Reduction, Title compound not separated from byproducts Petra, Danielle G. I.; Kamer, Paul C. J.; Spek, Anthony L.; Schoemaker, Hans E.; Van Leeuwen, Piet W. N. M.; Journal of Organic Chemistry; vol. 65; nb. 10; (2000); p. 3010 - 3017 View in Reaxys With potassium isopropoxide, (1S,3R,4R)-3-(hydroxymethyl)-2-azabicyclo<2.2.1>heptane, [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2 in isopropyl alcohol, Time= 1.5h, T= 20 °C , Hydrogenation, Title compound not separated from byproducts Alonso, Diego A.; Nordin, Sofia J. M.; Roth, Peter; Tarnai, Tibor; Andersson, Pher G.; Thommen, Marc; Pittelkow, Ulrich; Journal of Organic Chemistry; vol. 65; nb. 10; (2000); p. 3116 - 3122 View in Reaxys

138/258

2018-07-03 17:29:03

With sodium tetrahydroborate, (S)-diphenylprolinol, zirconium(IV) chloride in tetrahydrofuran, Time= 2h, T= 20 °C , Reduction, Product distribution Chary; Thomas; Iyengar; Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry; vol. 39; nb. 1; (2000); p. 57 - 59 View in Reaxys Stage 1: With diphenylsilane, bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate, (S,S)-2,2"-bis<(R)-1-(di(n-butyl)phosphino)ethyl>-1,1"-biferrocene in tetrahydrofuran, Time= 48h, T= -40 °C , hydrosilylation Stage 2: With methanol, potassium carbonate in tetrahydrofuran, Time= 4h, T= 20 °C , methanolysis, Title compound not separated from byproducts Kuwano, Ryoichi; Sawamura, Masaya; Shirai, Junya; Takahashi, Masatoshi; Ito, Yoshihiko; Bulletin of the Chemical Society of Japan; vol. 73; nb. 2; (2000); p. 485 - 496 View in Reaxys With sodium aluminum tetrahydride, (R,R)-(-)-IPTOL, (R)-1,1'-Bi-2-naphthol in tetrahydrofuran, Time= 24h, T= -70 °C , Reduction, Product distribution, Further Variations: Reagents, Solvents, Temperatures Vinogradov; Gorshkova; Pavlov; Mikhalev; Chel'tsova; Razmanov; Ferapontov; Malyshev; Heise; Russian Chemical Bulletin; vol. 49; nb. 3; (2000); p. 460 - 465 View in Reaxys With borane-THF, (S)-2-[(4-trifluoromethyl)anilinomethyl]indoline in tetrahydrofuran, Time= 2h, T= -15 °C Asami, Masatoshi; Sato, Shinsuke; Watanabe, Hiroyasu; Chemistry Letters; nb. 9; (2000); p. 990 - 991 View in Reaxys With potassium tert-butylate, [(η6-C6H6)Ru(μ-Cl)Cl]2, polymer 18 in isopropyl alcohol, Time= 24h, T= 70 °C , hydride transfer reduction Touchard, Francois; Fache, Fabienne; Lemaire, Marc; European Journal of Organic Chemistry; nb. 22; (2000); p. 3787 3792 View in Reaxys With potassium hydroxide, [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, (1R,2S)-1-Amino-2-indanol in isopropyl alcohol, Time= 1.5h, T= 20 °C , Title compound not separated from byproducts Wills, Martin; Palmer, Matthew; Smith, Athene; Kenny, Jennifer; Walsgrove, Tim; Molecules; vol. 5; nb. 1; (2000); p. 4 18 View in Reaxys With C10H19NO in tetrahydrofuran, Time= 2h, T= 20 °C , Reduction, Title compound not separated from byproducts Santhi; Rao, J.Madhusudana; Tetrahedron Asymmetry; vol. 11; nb. 17; (2000); p. 3553 - 3560 View in Reaxys With (R)-binaphthol, dimethylsulfide borane complex, aluminum isopropoxide in dichloromethane, Time= 0.166667h, T= 40 °C , Title compound not separated from byproducts Fu, I.-Pin; Uang, Biing-Jiun; Tetrahedron Asymmetry; vol. 12; nb. 1; (2001); p. 45 - 48 View in Reaxys With Rhizopus arrhizus in ethanol, Time= 168h, Title compound not separated from byproducts Salvi; Chattopadhyay; Tetrahedron; vol. 57; nb. 14; (2001); p. 2833 - 2839 View in Reaxys With trans-(1S,2S)-1-(methylamino)-2-indanol, dimethylsulfide borane complex in tetrahydrofuran, Time= 2h, T= 0 °C , Title compound not separated from byproducts Jones, Simon; Atherton; Tetrahedron Asymmetry; vol. 11; nb. 22; (2000); p. 4543 - 4548 View in Reaxys With borane-THF, (S)-2-[(4-trifluoromethyl)anilinomethyl]indoline in tetrahydrofuran, Time= 2h, T= -15 °C , Title compound not separated from byproducts

139/258

2018-07-03 17:29:03

Sato, Shinsuke; Watanabe, Hiroyasu; Asami, Masatoshi; Tetrahedron Asymmetry; vol. 11; nb. 21; (2000); p. 4329 - 4340 View in Reaxys With chiral diamine, tetramethylbiphenyl diisocyanate copolymer, [Ru(η6-toluene)Cl2]2, Time= 24h, T= 20 °C Saluzzo, Christine; Ter Halle, Rob; Touchard, Francois; Fache, Fabienne; Schulz, Emmanuelle; Lemaire, Marc; Journal of Organometallic Chemistry; vol. 603; nb. 1; (2000); p. 30 - 39 View in Reaxys With baker's yeast in water, Petroleum ether, Time= 24h, T= 20 °C , Enzymatic reaction, Title compound not separated from byproducts Liu; Zhu; Sun; Xu; Synthetic Communications; vol. 31; nb. 10; (2001); p. 1521 - 1526 View in Reaxys With titanium(IV) isopropylate, (1R,2R,4S,6S)-2-(2-anisyl)bicyclo<2.2.2>octane-2,6-diol, benzo[1,3,2]dioxaborole in tetrahydrofuran, Time= 24h, T= -20 °C , Title compound not separated from byproducts Sarvary, Ian; Almqvist, Fredrik; Frejd, Torbjoern; Chemistry - A European Journal; vol. 7; nb. 10; (2001); p. 2158 - 2166 View in Reaxys With formic acid, triethylamine, (2S)-N-phenylpyrrolidine-2-carboxamide, [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene) (chloride)(μ-chloride)]2 in dichloromethane, Time= 6h, T= 30 °C , Title compound not separated from byproducts Rhyoo, Hae Yoon; Yoon, Young-Ae; Park, Hee-Jung; Chung, Young Keun; Tetrahedron Letters; vol. 42; nb. 30; (2001); p. 5045 - 5048 View in Reaxys With dimethylsulfide borane complex, 3-mercapto-4-[(2'S)-2'-(diphenylhydroxymethyl)pyrrolidino]-3-cyclobutene-1,2-dione in toluene, Time= 1h, T= 50 °C , Title compound not separated from byproducts Zhang, Ji; Zhou, Hai-Bing; Lue, Shou-Mao; Luo, Mei-Ming; Xie, Ru-Gang; Choi, Michael C.K.; Zhou, Zhong-Yuan; Chan, Albert S.C.; Yang, Teng-Kuei; Tetrahedron Asymmetry; vol. 12; nb. 13; (2001); p. 1907 - 1912 View in Reaxys With sodium aluminum tetrahydride, (S)-diphenylprolinol in tetrahydrofuran, Time= 3h, T= -70 °C , Title compound not separated from byproducts Vinogradov; Mikhalev; Pavlov; Ferapontov; Malyshev; Heise; Russian Chemical Bulletin; vol. 50; nb. 5; (2001); p. 843 845 View in Reaxys With chloro(1,5-cyclooctadiene)rhodium(I) dimer, isopropyl alcohol, (1S,2S)-N,N'-dibenzylidene-1,2-diaminocyclohexane, Time= 120h, T= 20 °C , Product distribution, Further Variations: Reagents, substrates Pavlov; Vinogradov; Starodubtseva; Chel'tsova; Ferapontov; Malyshev; Heise; Russian Chemical Bulletin; vol. 50; nb. 4; (2001); p. 734 - 735 View in Reaxys With 9-borabicyclo[3.3.1]nonane dimer, borane-THF, (S)-diphenylprolinol in tetrahydrofuran, Time= 1h, T= 20 °C , Title compound not separated from byproducts Kanth, Josyula V.B.; Brown, Herbert C.; Tetrahedron; vol. 58; nb. 6; (2002); p. 1069 - 1074 View in Reaxys Stage 1: With copper (II)-fluoride, phenylsilane, (S)-(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine) in toluene, Time= 9h, T= 20 °C Stage 2: With hydrogenchloride, Title compound not separated from byproducts Sirol, Sabine; Courmarcel, James; Mostefai, Naouel; Riant, Olivier; Organic Letters; vol. 3; nb. 25; (2001); p. 4111 - 4113 View in Reaxys Stage 1: With aluminum isopropoxide, (Ra)-5,6,7,8,5',6',7',8'-octahydro-[1,1']binaphthalenyl-2,2'-diol in dichloromethane, Time= 0.5h, T= 20 °C Stage 2: With dimethylsulfide borane complex in dichloromethane, Time= 0.166667h, T= 40 °C , Title compound not separated from byproducts

140/258

2018-07-03 17:29:03

Lin, Yang-Miin; Fu, I-Pin; Uang, Biing-Jiun; Tetrahedron Asymmetry; vol. 12; nb. 23; (2001); p. 3217 - 3221 View in Reaxys With 4,4'-dibenzyl-2,2'-dimethyl-5,5'-bi-1,3,2-oxazaborolidine in tetrahydrofuran, Time= 1h, Product distribution, Further Variations: Reagents Jiang, Biao; Feng, Yan; Hang, Jian-Feng; Tetrahedron Asymmetry; vol. 12; nb. 16; (2001); p. 2323 - 2329 View in Reaxys With potassium hydroxide, (1R,2S)-1-Amino-2-indanol, [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2 in isopropyl alcohol, Time= 1.5h, T= 20 °C , Product distribution, Further Variations: Temperatures, Reagents, time Palmer, Matthew J.; Kenny, Jennifer A.; Walsgrove, Tim; Kawamoto, Aparecida M.; Wills, Martin; Journal of the Chemical Society. Perkin Transactions 1; nb. 3; (2002); p. 416 - 427 View in Reaxys With potassium hydroxide, isopropyl alcohol, bis(1,5-cyclooctadiene)diiridium(I) dichloride, (R,R)-(salen) ligand in various solvent(s), Time= 24h, T= 70 °C , Title compound not separated from byproducts Maillard, David; Pozzi, Gianluca; Quici, Silvio; Sinou, Denis; Tetrahedron; vol. 58; nb. 20; (2002); p. 3971 - 3976 View in Reaxys With potassium hydroxide, isopropyl alcohol, (4S)-4,5-dihydro-4-phenyl-2-(1,2,3,4-tetrahydroquinolin-8-yl)oxazole, [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, Time= 37h, T= -20 °C , Title compound not separated from byproducts Zhou, Yi-Bo; Tang, Fang-Yi; Xu, Hua-Dong; Wu, Xin-Yan; Ma, Jun-An; Zhou, Qi-Lin; Tetrahedron Asymmetry; vol. 13; nb. 5; (2002); p. 469 - 473 View in Reaxys With borane-THF, (1S,2S)-2-amino-1-ferrocenyl-3,3-dimethyl-1-butanol in tetrahydrofuran, T= 30 °C , Title compound not separated from byproducts Brunin, Thierry; Cabou, Jerome; Bastin, Stephanie; Brocard, Jacques; Pelinski, Lydie; Tetrahedron Asymmetry; vol. 13; nb. 12; (2002); p. 1241 - 1243 View in Reaxys With sodium hydroxide, (1R,2R)-(+)-N,N'-dimethylcyclohexene-1,2-diamine, tris(triphenylphosphine)ruthenium(II) chloride in isopropyl alcohol, Time= 3h, T= 82 °C , Product distribution, Further Variations: Reagents, Catalysts, Temperatures, time Kim, Geon-Joong; Kim, Sang-Han; Chong, Pong-Hyun; Kwon, Mi-Ae; Tetrahedron Letters; vol. 43; nb. 45; (2002); p. 8059 - 8062 View in Reaxys With sodium hydroxide, (R,R)-N,N'-dimethyl-1,2-diaminocyclohexane, (2-formylphenyl)(diphenyl)phosphine, tris(triphenylphosphine)ruthenium(II) chloride in isopropyl alcohol, Time= 3h, T= 82 °C Kim, Geon-Joong; Kim, Sang-Han; Chong, Pong-Hyun; Kwon, Mi-Ae; Tetrahedron Letters; vol. 43; nb. 45; (2002); p. 8059 - 8062 View in Reaxys With copper (II)-fluoride, phenylsilane, (S)-(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine) in toluene, Time= 9h, T= 20 °C , Title compound not separated from byproducts Courmarcel, James; Mostefai, Naouel; Sirol, Sabine; Choppin, Sabine; Riant, Olivier; Israel Journal of Chemistry; vol. 41; nb. 4; (2001); p. 231 - 240 View in Reaxys With (S,S)-N,N'-bis[o-(diphenylphosphino)benzylidene]-1,2-diaminocyclohexane, potassium isopropoxide, isopropyl alcohol, dodecacarbonyl-triangulo-triruthenium, Time= 4h, T= 40 °C , Product distribution, Further Variations: Reagents, reaction time Zhang, Hui; Yang, Chuan-Bo; Li, Yan-Yun; Donga, Zhen-Rong; Gao, Jing-Xing; Nakamura, Hideaki; Murata, Kunihiko; Ikariya, Takao; Chemical Communications; nb. 1; (2003); p. 142 - 143 View in Reaxys

141/258

2018-07-03 17:29:03

With (-)-C5Me5FeC10H10N, phenyl(2,4,6-trimethylphenyl)silane, chloro(1,5-cyclooctadiene)rhodium(I) dimer in tetrahydrofuran, Time= 72h, T= 20 °C , Title compound not separated from byproducts Tao, Beata; Fu, Gregory C.; Angewandte Chemie - International Edition; vol. 41; nb. 20; (2002); p. 3892 - 3894 View in Reaxys Stage 1: With (((1S,2S)-2-t-BuS-c-hexyloxy)PPh2)-(2,5-norbornadiene)RhOTf, 1-naphthylphenylsilane in tetrahydrofuran, Time= 12h, T= -20 °C Stage 2: With methanol in tetrahydrofuran, Time= 0.5h, T= 20 °C , Title compound not separated from byproducts Evans, David A.; Michael, Forrest E.; Tedrow, Jason S.; Campos, Kevin R.; Journal of the American Chemical Society; vol. 125; nb. 12; (2003); p. 3534 - 3543 View in Reaxys With (S,SP)-2-[2-Pcy2]cyrhetrenyl-4-t-Bu-4,5-di(H)-1,3-oxazole, potassium tert-butylate, tris(triphenylphosphine)ruthenium(II) chloride in isopropyl alcohol, Time= 2h, T= 82 °C , Product distribution, Further Variations: Catalysts, Temperatures, time Bolm, Carsten; Xiao, Li; Kesselgruber, Martin; Organic and Biomolecular Chemistry; vol. 1; nb. 1; (2003); p. 145 - 152 View in Reaxys With titanium 3,4-di-O-benzyl-D-mannitol trimer, benzo[1,3,2]dioxaborole in dichloromethane, T= -20 °C , Title compound not separated from byproducts Hegarty, Philip; Lau, Raymond; Motherwell, William B.; Tetrahedron Letters; vol. 44; nb. 9; (2003); p. 1851 - 1853 View in Reaxys With N-tert-butyl-N-trimethylsilylamine-borane, (3aR)-1-methyl-3,3-diphenyl-tetrahydro-pyrrolo[1,2-c][1,3,2]oxazaborole in toluene, T= 22 °C Huertas, Ramon E.; Corella, Joseph A.; Soderquist, John A.; Tetrahedron Letters; vol. 44; nb. 24; (2003); p. 4435 - 4437 View in Reaxys With Zr[Ru((R)-L1)(DPEN)Cl2]*4H2O, potassium tert-butylate, hydrogen in isopropyl alcohol, Time= 20h, p= 36200.4Torr , Title compound not separated from byproducts Hu, Aiguo; Ngo, Helen L.; Lin, Wenbin; Journal of the American Chemical Society; vol. 125; nb. 38; (2003); p. 11490 11491 View in Reaxys With potassium isopropoxide, [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, chiral (aminoalkyl)phosphane in isopropyl alcohol, T= 60 °C , Title compound not separated from byproducts Leautey, Matthieu; Jubault, Philippe; Pannecoucke, Xavier; Quirion, Jean-Charles; European Journal of Organic Chemistry; nb. 19; (2003); p. 3761 - 3768 View in Reaxys With sodium aluminum tetrahydride, (R,R)-TADDOL in tetrahydrofuran, T= -70 °C , Title compound not separated from byproducts Vinogradov; Gorshkova; Chel'tsova; Pavlov; Razmanov; Ferapontov; Malyshev; Heise; Russian Chemical Bulletin; vol. 52; nb. 2; (2003); p. 471 - 479 View in Reaxys With sodium aluminum tetrahydride, (S,S)-taddol in tetrahydrofuran, T= -70 °C , Title compound not separated from byproducts Vinogradov; Gorshkova; Chel'tsova; Pavlov; Razmanov; Ferapontov; Malyshev; Heise; Russian Chemical Bulletin; vol. 52; nb. 2; (2003); p. 471 - 479 View in Reaxys With borane, methyl (S)-pyroglutamate in tetrahydrofuran, Time= 0.166667h, T= 20 °C , Title compound not separated from byproducts Kawanami, Yasuhiro; Murao, Shinichi; Ohga, Takahiko; Kobayashi, Nobuyo; Tetrahedron; vol. 59; nb. 42; (2003); p. 8411 - 8414

142/258

2018-07-03 17:29:03

View in Reaxys With dimethylsulfide borane complex, polymer-supported η,η-diphenyl-L-prolinol in tetrahydrofuran, T= 22 °C , Product distribution, Further Variations: Reagents Kell, Roger J.; Hodge, Philip; Snedden, Peter; Watson, David; Organic and Biomolecular Chemistry; vol. 1; nb. 18; (2003); p. 3238 - 3243 View in Reaxys With potassium tert-butylate, hydrogen, polymer-supported chiral 1,2-diphenylethylenediamine in isopropyl alcohol, Time= 4h, T= 20 °C , p= 7500.6Torr , Title compound not separated from byproducts Li, Xiaoguang; Chen, Weiping; Hems, William; King, Frank; Xiao, Jianliang; Organic Letters; vol. 5; nb. 24; (2003); p. 4559 - 4561 View in Reaxys With -methyl-2-oxoethyl)carbamate, tert-butyl N-((1S)-2-{[(1R)-2-hydroxy-1-phenylethyl]amino}-1, isopropyl alcohol, sodium hydroxide, [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, Time= 5h, T= 20 °C , Title compound not separated from byproducts Pastor, Isidro M.; Vaestilae, Patrik; Adolfsson, Hans; Chemistry - A European Journal; vol. 9; nb. 17; (2003); p. 4031 - 4045 View in Reaxys With dimethylsulfide borane complex, chiral N-P=O framework containing cyclic ligand in toluene, Time= 1h, T= 110 °C , Title compound not separated from byproducts Basavaiah, Deevi; Reddy, Gone Jayapal; Chandrashekar, Vanampally; Tetrahedron Asymmetry; vol. 15; nb. 1; (2004); p. 47 - 52 View in Reaxys With dimethylsulfide borane complex in tetrahydrofuran, Heating, Title compound not separated from byproducts Zhang, Yong-Xin; Du, Da-Ming; Chen, Xiao; Lue, Shao-Feng; Hua, Wen-Ting; Tetrahedron Asymmetry; vol. 15; nb. 1; (2004); p. 177 - 182 View in Reaxys Stage 1: With copper diacetate, phenylsilane, (S)-(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine) in toluene, Time= 1h, T= 0 °C Stage 2: With tetrabutyl ammonium fluoride in tetrahydrofuran, diethyl ether, Time= 0.5h Lee, Dong-Won; Yun, Jaesook; Tetrahedron Letters; vol. 45; nb. 28; (2004); p. 5415 - 5417 View in Reaxys With borane-THF, (R,S)-C37H30NO3B in tetrahydrofuran, Time= 2h, T= 0 - 5 °C , Product distribution, Further Variations: Reagents Liu, Dejun; Shan, Zixing; Zhou, Yan; Wu, Xiaojun; Qin, Jingui; Helvetica Chimica Acta; vol. 87; nb. 9; (2004); p. 2310 2317 View in Reaxys Stage 1: With (S,S)-2,2"-bis<(diethylphosphino)methyl>-1,1"-biferrocene, bis(3-fluorophenyl)silane, bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate in tetrahydrofuran, Time= 24h, T= -40 °C Stage 2: With methanol, potassium carbonate in tetrahydrofuran, Time= 4h, T= 20 °C , Title compound not separated from byproducts Kuwano, Ryoichi; Uemura, Takashi; Saitoh, Makoto; Ito, Yoshihiko; Tetrahedron Asymmetry; vol. 15; nb. 14; (2004); p. 2263 - 2271 View in Reaxys With sodium hydroxide, isopropyl alcohol, cis-[RuCl2(P(i-Pr)3){η3-N,N,N-(R,R)-Ph-pybox}], Time= 0.0833333h, T= 82 °C , Title compound not separated from byproducts Cuervo, Dario; Gamasa, M. Pilar; Gimeno, Jose; Chemistry - A European Journal; vol. 10; nb. 2; (2004); p. 425 - 432 View in Reaxys

143/258

2018-07-03 17:29:03

With potassium hydroxide, chiral norephedrine-terminated polymer, [Ru(p-cumene)Cl2]2 in isopropyl alcohol, Title compound not separated from byproducts Bastin, Stephanie; Eaves, Richard J.; Edwards, Christopher W.; Ichihara, Osamu; Whittaker, Mark; Wills, Martin; Journal of Organic Chemistry; vol. 69; nb. 16; (2004); p. 5405 - 5412 View in Reaxys With Trimethyl borate, dimethylsulfide borane complex, (1R,2S)-1-Amino-2-indanol in tetrahydrofuran, Time= 0.5h, T= 20 °C , Title compound not separated from byproducts Gilmore, Nathan J.; Jones, Simon; Muldowney, Mark P.; Organic Letters; vol. 6; nb. 16; (2004); p. 2805 - 2808 View in Reaxys With potassium hydroxide, isopropyl alcohol, (Rp,1R,2S)-2-[2-[(tert-butyl)(phenyl)phosphinoyl]ethylamino]-1-phenylpropan-1ol, [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, Time= 2h, T= 29 °C , Title compound not separated from byproducts Cheng, Xiaohui; Horton, Peter N.; Hursthouse, Michael B.; Hii, King Kuok; Tetrahedron Asymmetry; vol. 15; nb. 14; (2004); p. 2241 - 2246 View in Reaxys Stage 1: With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, N-[2-(diphenylphosphinoyl)ethyl]-(1R,2S)-norephedrine, isopropyl alcohol, Time= 0.5h, T= 83 °C Stage 2: With potassium hydroxide, Time= 2h, T= 29 °C , Title compound not separated from byproducts Rahman, Mohammed S.; Oliana, Marco; Hii, King Kuok; Tetrahedron Asymmetry; vol. 15; nb. 12; (2004); p. 1835 - 1840 View in Reaxys With dimethylsulfide borane complex, chiral 1,3-diaza-2-phospha-2-oxobicyclo[3.3.0]octane in toluene, Time= 0.75h, T= 110 °C , Title compound not separated from byproducts Basavaiah, Deevi; Reddy, Gone Jayapal; Rao, Kalapala Venkateswara; Tetrahedron Asymmetry; vol. 15; nb. 12; (2004); p. 1881 - 1888 View in Reaxys With Ru-SB-SDPEN-MCM-48, potassium tert-butylate, hydrogen in isopropyl alcohol, Time= 4h, T= 100 °C , p= 10350.8Torr Ghosh, Anirban; Kumar, Rajiv; Journal of Catalysis; vol. 228; nb. 2; (2004); p. 386 - 396 View in Reaxys With N-(p-toluenesulfonyl)-(1R,2R)-diphenylethylenediamine, sodium formate, [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, Time= 2h, T= 40 °C , Title compound not separated from byproducts Wu, Xiaofeng; Li, Xiaoguang; Hems, William; King, Frank; Xiao, Jianliang; Organic and Biomolecular Chemistry; vol. 2; nb. 13; (2004); p. 1818 - 1821 View in Reaxys With potassium tert-butylate, hydrogen, bisphosphonic acid-derived Ru(BINAP)(DPEN)Cl2 in isopropyl alcohol, Time= 24h, p= 36200.4Torr , Title compound not separated from byproducts Ngo, Helen L.; Hu, Aiguo; Lin, Wenbin; Tetrahedron Letters; vol. 46; nb. 4; (2005); p. 595 - 597 View in Reaxys With dimethylsulfide borane complex, (+)-3-exo-amino-7,7-dimethoxynorbornan-2-exo-ol in tetrahydrofuran, Time= 2h, T= 20 °C , Title compound not separated from byproducts Lapis, Alexandre A. M.; De Fatima, Angelo; Martins, Jose E. D.; Costa, Valentim E. U.; Pilli, Ronaldo A.; Tetrahedron Letters; vol. 46; nb. 3; (2005); p. 495 - 498 View in Reaxys With sodium hydroxide, isopropyl alcohol, tris(triphenylphosphine)ruthenium(II) chloride, (S)-(+)-2-(2-diphenylarsinophenyl)-4-(isopropyl)oxazoline, Time= 4h, Heating, Title compound not separated from byproducts Tan, Duan-Ming; Chan, Kin Shing; Tetrahedron Letters; vol. 46; nb. 3; (2005); p. 503 - 505 View in Reaxys

144/258

2018-07-03 17:29:03

With (S)-diphenylprolinol, dimethylsulfide borane complex in tetrahydrofuran, toluene, T= 25 °C , Title compound not separated from byproducts Xu, Jiaxi; Wei, Tiezheng; Zhang, Qihan; Journal of Organic Chemistry; vol. 69; nb. 20; (2004); p. 6860 - 6866 View in Reaxys With triethylammonium formate, chiral 'roofed' cis-diamine-Ru(II), Time= 17h, T= 25 °C , Title compound not separated from byproducts Matsunaga, Hirofumi; Ishizuka, Tadao; Kunieda, Takehisa; Tetrahedron Letters; vol. 46; nb. 21; (2005); p. 3645 - 3648 View in Reaxys With (R,R,R,R)-N,N,N',N'-(2-OH-2-(Ph)ethyl)4-1,3-xylylenediamine, SmI(η8-cyclooctatetraene)(thf), isopropyl alcohol, Time= 48h, T= 25 °C , Title compound not separated from byproducts Ohno, Kouji; Kataoka, Yasutaka; Mashima, Kazushi; Organic Letters; vol. 6; nb. 25; (2004); p. 4695 - 4697 View in Reaxys With mono-[6-2(S)-hydroxypropylamino-6-deoxy]-η-cyclodextrin, sodium formate, [(η6-C6H6)Ru(μ-Cl)Cl]2 in water, N,N-dimethyl-formamide, Time= 24h, T= 20 °C , Title compound not separated from byproducts Schlatter, Alain; Kundu, Mrinal K.; Woggon, Wolf-D.; Angewandte Chemie - International Edition; vol. 43; nb. 48; (2004); p. 6731 - 6734 View in Reaxys With SiO2-supported (R,R)-1,2-diphenylethylenediamine-derivative, triethylamine carbonate, triethylamine, [ruthenium(II)(η6-1methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, Time= 28h, T= 40 °C , Title compound not separated from byproducts Liu, Pei-Nian; Gu, Pei-Ming; Deng, Jin-Gen; Tu, Yong-Qiang; Ma, Ya-Ping; European Journal of Organic Chemistry; nb. 15; (2005); p. 3221 - 3227 View in Reaxys With potassium hydroxide, (3S,3'S)-3,3'-bimorpholine, chloro(1,5-cyclooctadiene)rhodium(I) dimer in isopropyl alcohol, Time= 21h, T= 20 °C , Product distribution Kriis, Kadri; Kanger, Tonis; Lopp, Margus; Tetrahedron Asymmetry; vol. 15; nb. 17; (2004); p. 2687 - 2691 View in Reaxys With C49H47O2N2 (1+)*BF4 (1-), diphenylsilane, silver trifluoromethanesulfonate, tris(triphenylphosphine)ruthenium(II) chloride in tetrahydrofuran, Time= 16h, T= 0 °C , Title compound not separated from byproducts Song, Chun; Ma, Changqin; Ma, Yudao; Feng, Wenhua; Ma, Shutao; Chai, Qiang; Andrus, Merritt B.; Tetrahedron Letters; vol. 46; nb. 18; (2005); p. 3241 - 3244 View in Reaxys With potassium tert-butylate, hydrogen, chiral ruthenium(II) complex in isopropyl alcohol, Time= 7h, T= 0 °C , p= 52504.2Torr , Title compound not separated from byproducts Xu, Yingjian; Clarkson, Guy C.; Docherty, Gordon; North, Carl L.; Woodward, Gary; Wills, Martin; Journal of Organic Chemistry; vol. 70; nb. 20; (2005); p. 8079 - 8087 View in Reaxys With borane-THF, bis-(4-heptadecafluorooctyl-phenyl)-pyrrolidin-2-yl-methanol in tetrahydrofuran, Time= 0.5h, T= 20 °C , Title compound not separated from byproducts Dalicsek, Zoltan; Pollreisz, Ferenc; Goemoery, Agnes; Soos, Tibor; Organic Letters; vol. 7; nb. 15; (2005); p. 3243 - 3246 View in Reaxys With carbonylhydridotris(triphenylphosphine)iridium(I), N,N'-bis[o-(diphenylphosphino)benzylidene]-1R,2R-diaminocyclohexane in isopropyl alcohol, Time= 0.5h, T= 75 °C , Title compound not separated from byproducts Dong, Zhen-Rong; Li, Yan-Yun; Chen, Jian-Shan; Li, Bao-Zhu; Xing, Yan; Gao, Jing-Xing; Organic Letters; vol. 7; nb. 6; (2005); p. 1043 - 1045 View in Reaxys

145/258

2018-07-03 17:29:03

With potassium hydroxide, [BMIM](1+)*[p-CH3C6H4SO3](1-), hydrogen, (S,S)-DPENDS, [RuCl2(TPPTS)2]2, Time= 0.5h, T= 50 °C , p= 37503Torr , Title compound not separated from byproducts Xiong, Wei; Lin, Qi; Ma, Hongxia; Zheng, Hongjie; Chen, Hua; Li, Xianjun; Tetrahedron Asymmetry; vol. 16; nb. 11; (2005); p. 1959 - 1962 View in Reaxys With sodium formate, cetyltrimethylammonim bromide, Noyori's catalyst in water, Time= 24h, T= 28 °C , Title compound not separated from byproducts Wang, Fei; Liu, Hui; Cun, Linfeng; Zhu, Jin; Deng, Jingen; Jiang, Yaozhong; Journal of Organic Chemistry; vol. 70; nb. 23; (2005); p. 9424 - 9429 View in Reaxys With formic acid, triethylamine, Time= 3h, T= 40 °C , Title compound not separated from byproducts Hayes, Aidan M.; Morris, David J.; Clarkson, Guy J.; Wills, Martin; Journal of the American Chemical Society; vol. 127; nb. 20; (2005); p. 7318 - 7319 View in Reaxys With [(R,R,R)-Ru(BINAP-PO3H2)(DPEN)Cl2] on magnetite nanoparticle, potassium tert-butylate, hydrogen in isopropyl alcohol, Time= 20h, T= 20 °C , p= 36200.4Torr , Title compound not separated from byproducts Hu, Aiguo; Yee, Gordon T.; Lin, Wenbin; Journal of the American Chemical Society; vol. 127; nb. 36; (2005); p. 12486 12487 View in Reaxys With sodium tetrahydroborate, 2-(3-nitrophenyl)-1,3,2-dioxaborolane-(4R,5R)-dicarboxylic acid in tetrahydrofuran, Time= 0.5h Cordes, David B.; Nguyen, Thao M.; Kwong, Tracey J.; Suri, Jeff T.; Luibrand, Richard T.; Singaram, Bakthan; European Journal of Organic Chemistry; nb. 24; (2005); p. 5289 - 5295 View in Reaxys With sodium hydroxide, (S(P))-2-(2-(diphenylphosphino)ferrocenyl)-4-(1-methylethyl)-4,5-dihydrooxazole, hydrogen, tris(triphenylphosphine)ruthenium(II) chloride in toluene, Time= 1h, T= 20 °C , p= 60004.8Torr , Title compound not separated from byproducts Naud, Frederic; Malan, Christophe; Spindler, Felix; Rueggeberg, Carsten; Schmidt, Andreas T.; Blaser, Hans-Ulrich; Advanced Synthesis and Catalysis; vol. 348; nb. 1-2; (2006); p. 47 - 50 View in Reaxys With cis-1R, 2S-2-N-benzylaminocyclohexyl-1-methanol, isopropyl alcohol, [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene) (chloride)(μ-chloride)]2, Time= 6h, T= 20 °C , Title compound not separated from byproducts Schiffers, Ingo; Rantanen, Toni; Schmidt, Frank; Bergmans, Werner; Zani, Lorenzo; Bolm, Carsten; Journal of Organic Chemistry; vol. 71; nb. 6; (2006); p. 2320 - 2331 View in Reaxys With potassium hydroxide, chiral hydroxyaminophosphine oxide ligand, isopropyl alcohol, [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, Time= 1h, T= 29 °C , Title compound not separated from byproducts Oliana, Marco; King, Frank; Horton, Peter N.; Hursthouse; Hii, King Kuok; Journal of Organic Chemistry; vol. 71; nb. 6; (2006); p. 2472 - 2479 View in Reaxys With formic acid, imidazolium salt unit attached to (1S,2S)-TsDPEN, triethylamine, [(η6-C6H6)Ru(μ-Cl)Cl]2, 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate, Time= 44h, T= 20 °C , Title compound not separated from byproducts Kawasaki, Ikuo; Tsunoda, Kazuya; Tsuji, Tomoko; Yamaguchi, Tomoko; Shibuta, Hiroki; Uchida, Nozomi; Yamashita, Masayuki; Ohta, Shunsaku; Chemical Communications; nb. 16; (2005); p. 2134 - 2136 View in Reaxys With lithium aluminium tetrahydride, 1-ethyl-pyridinium trifluoroacetate, (R)-6,6'-dibromo-1,1'-binaphth-2-ol, T= 0 - 45 °C , Title compound not separated from byproducts

146/258

2018-07-03 17:29:03

Xiao, Ying; Malhotra, Sanjay V.; Tetrahedron Asymmetry; vol. 17; nb. 7; (2006); p. 1062 - 1065 View in Reaxys With methyl N-formyl-η'-(2,4,6-triethylphenyl)-L-proline, trichlorosilane in chloroform, Time= 6h, T= 20 °C , Title compound not separated from byproducts Matsumura, Yoshihiro; Ogura, Kanako; Kouchi, Yoshimi; Iwasaki, Fumiaki; Onomura, Osamu; Organic Letters; vol. 8; nb. 17; (2006); p. 3789 - 3792 View in Reaxys With AMBERLITE XAD-7, Cyanidium caldarium cultured cells in water, Time= 120h, T= 42 °C , pH= 2.5, Irradiation, Title compound not separated from byproducts Utsukihara, Takamitsu; Misumi, Osami; Kato, Nakahide; Kuroiwa, Tsuneyoshi; Horiuchi, C. Akira; Tetrahedron Asymmetry; vol. 17; nb. 8; (2006); p. 1179 - 1185 View in Reaxys With sodium hydroxide, 9,9-dimethylxanthene-4,5-diyl-bis{[chiral-BINOL]phosphonite}, isopropyl alcohol, [ruthenium(II)(η6-1methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, Time= 26h, T= 40 °C , Title compound not separated from byproducts Reetz, Manfred T.; Li, Xiaoguang; Journal of the American Chemical Society; vol. 128; nb. 4; (2006); p. 1044 - 1045 View in Reaxys With potassium isopropoxide, chiral (aminoalkyl)phosphane in isopropyl alcohol, T= 60 °C , Title compound not separated from byproducts Leautey, Matthieu; Jubault, Philippe; Pannecoucke, Xavier; Quirion, Jean-Charles; European Journal of Organic Chemistry; nb. 19; (2003); p. 3761 - 3768 View in Reaxys With potassium hydroxide, 9-amino-9-deoxyepicinchonine, bis(1,5-cyclooctadiene)diiridium(I) dichloride in isopropyl alcohol, Time= 48h, T= -20 °C , Title compound not separated from byproducts He, Wei; Zhang, Bang-Le; Jiang, Ru; Liu, Peng; Sun, Xiao-Li; Zhang, Sheng-Yong; Tetrahedron Letters; vol. 47; nb. 30; (2006); p. 5367 - 5370 View in Reaxys With (S)-diphenylprolinol, tetrabutylammonium borohydride, methyl iodide in tetrahydrofuran, Time= 0.5h, T= 25 °C , Title compound not separated from byproducts Anwar, Shaik; Periasamy, Mariappan; Tetrahedron Asymmetry; vol. 17; nb. 23; (2006); p. 3244 - 3247 View in Reaxys With (S)-(+)-2-(5-phenyl-4,5-dihydro-1,3-oxazol-2-yl)pyridine, trichlorosilane in chloroform, Time= 24h, T= -20 °C , Title compound not separated from byproducts Malkov, Andrei V.; Stewart Liddon, Angus J. P.; Ramirez-Lopez, Pedro; Bendova, Lada; Haigh, David; Kocovsky, Pavel; Angewandte Chemie - International Edition; vol. 45; nb. 9; (2006); p. 1432 - 1435 View in Reaxys With air, sodium formate, Ru-(1R,2R)-N-(p-toluenesulfonyl)-1,2-cyclohexanediamine, Time= 1h, T= 40 °C , Title compound not separated from byproducts Wu, Xiaofeng; Vinci, Daniele; Ikariya, Takao; Xiao, Jiangliang; Chemical Communications; nb. 35; (2005); p. 4447 - 4449 View in Reaxys With 4 A molecular sieve, (1R,2R,4S,6S)-2-(2-anisyl)bicyclo<2.2.2>octane-2,6-diol, benzo[1,3,2]dioxaborole, titanium(IV) isopropylate in tetrahydrofuran, Time= 24h, T= -20 °C , Title compound not separated from byproducts Sarvary, Ian; Almqvist, Fredrik; Frejd, Torbjoern; Chemistry - A European Journal; vol. 7; nb. 10; (2001); p. 2158 - 2166 View in Reaxys With N,N'-bis[(1R,2R)-2-aminocyclohexyl]benzene-1,3-disulfonamide, water, sodium formate, dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer, air, Time= 0.25h, T= 40 °C , Title compound not separated from byproducts Cortez, Norma A.; Rodriguez-Apodaca, Ramon; Aguirre, Gerardo; Parra-Hake, Miguel; Cole, Thomas; Somanathan, Ratnasamy; Tetrahedron Letters; vol. 47; nb. 48; (2006); p. 8515 - 8518

147/258

2018-07-03 17:29:03

View in Reaxys With formic acid, triethylamine, [((R,R)-N-(1,2,6-triphenyl-3-azahexyl)tosylamide*HCl)RuCl2]2, Time= 3h, T= 40 °C , Title compound not separated from byproducts Morris, David J.; Hayes, Aidan M.; Wills, Martin; Journal of Organic Chemistry; vol. 71; nb. 18; (2006); p. 7035 - 7044 View in Reaxys With lithium tetrahydridogallate, benzo[1,3,2]dioxaborole, (R)-S,O-chelate 2-hydroxy-2'-mercapto-1,1'-binaphthyl in tetrahydrofuran, diethyl ether, Time= 18h, T= -25 °C , Title compound not separated from byproducts. Blake, Alexander J.; Cunningham, Anthony; Ford, Alan; Teat, Simon J.; Woodward, Simon; Chemistry - A European Journal; vol. 6; nb. 19; (2000); p. 3586 - 3594 View in Reaxys With Geotrichum candidum IFO 4597 in water, Time= 24h, T= 30 °C , Microbiological reaction, Reduction, Product distribution, Further Variations: Reagents Nakamura, Kaoru; Fujii, Mikio; Ida, Yoshiteru; Journal of the Chemical Society, Perkin Transactions 1; nb. 19; (2000); p. 3205 - 3211 View in Reaxys With polymethylhydrosiloxane, (S,S,S,S)-N,N'-di(η-phenylethyl)cyclohexane-1,2-diamine, diethylzinc in toluene, Time= 24h, T= 20 °C , Title compound not separated from byproducts. Mastranzo, Virginia M.; Quintero, Leticia; De Parrodi, Cecilia Anaya; Juaristi, Eusebio; Walsh, Patrick J.; Tetrahedron; vol. 60; nb. 8; (2004); p. 1781 - 1789 View in Reaxys With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, (R,R)-1,2-bis(3',3"-PEG-oxyphenyl)-1-amino-2(TsNH)-ethylene in formic acid, triethylamine, Time= 30h, T= 50 °C Li, Xiaoguang; Chen, Weiping; Hems, William; King, Frank; Xiao, Jianliang; Tetrahedron Letters; vol. 45; nb. 5; (2004); p. 951 - 953 View in Reaxys With [IrHCl2(cod)]2, N,N'-bis[o-(diphenylphosphino)benzylidene]-1R,2R-diaminocyclohexane in isopropyl alcohol, Time= 2h, T= 20 °C , Title compound not separated from byproducts. Chen, Jian-Shan; Li, Yan-Yun; Dong, Zhen-Rong; Li, Bao-Zhu; Gao, Jing-Xing; Tetrahedron Letters; vol. 45; nb. 45; (2004); p. 8415 - 8418 View in Reaxys With potassium hydroxide, isopropyl alcohol, air, [IrHCl2(cod)]2, Time= 1.5h, T= 25 °C , Title compound not separated from byproducts. Shen, Wei-Yi; Zhang, Hui; Zhang, Hua-Lin; Gao, Jing-Xing; Tetrahedron Asymmetry; vol. 18; nb. 6; (2007); p. 729 - 733 View in Reaxys With potassium tert-butylate, polymer-supported (S,S)-1,2-diphenylethylenediamine, RuCl2/(S)-BINAP(dmf)n in N,N-dimethyl-formamide, isopropyl alcohol, tert-butyl alcohol, Time= 1h, p= 7500.75Torr Itsuno, Shinichi; Chiba, Masahiro; Takahashi, Miyuki; Arakawa, Yukihiro; Haraguchi, Naoki; Journal of Organometallic Chemistry; vol. 692; nb. 1-3; (2007); p. 487 - 494 View in Reaxys With hydrogen in tetrahydrofuran, Time= 4h, T= 20 °C , p= 7500.75Torr , Title compound not separated from byproducts. Adair, Gareth R. A.; Williams, Jonathan M. J.; Chemical Communications; nb. 25; (2007); p. 2608 - 2609 View in Reaxys With sodium formate, chiral monosulfonamide-cyclohexane-1,2-diamine-RhCp* complex in water, Time= 6h, T= 40 °C , Title compound not separated from byproducts. Cortez, Norma A.; Aguirre, Gerardo; Parra-Hake, Miguel; Somanathan, Ratnasamy; Tetrahedron Letters; vol. 48; nb. 25; (2007); p. 4335 - 4338

148/258

2018-07-03 17:29:03

View in Reaxys With potassium hydroxide, IrCl(COD)PPh3 in isopropyl alcohol, Time= 8h, T= 25 °C , Title compound not separated from byproducts. Zhang, Xue-Qin; Li, Yan-Yun; Zhang, Hui; Gao, Jing-Xing; Tetrahedron Asymmetry; vol. 18; nb. 17; (2007); p. 2049 - 2054 View in Reaxys With dimethylsulfide borane complex, (R)-CPh2(OH)-CH(NH2)-CH2-O-(t-BuMe2Si) in tetrahydrofuran, Time= 0.0833333h, T= 50 °C , Product distribution, Further Variations: Catalysts Vatmurge, Namdev S.; Hazra, Braja G.; Pore, Vandana S.; Australian Journal of Chemistry; vol. 60; nb. 3; (2007); p. 196 204 View in Reaxys With potassium hydroxide, hydrogen, [P(m-C6H4SO3Na)3]-stabilized ruthenium in water, Time= 1.33333h, T= 30 °C , p= 37503.8Torr , Title compound not separated from byproducts. Wang, Jinbo; Feng, Jian; Qin, Ruixiang; Fu, Haiyan; Yuan, Maolin; Chen, Hua; Li, Xianjun; Tetrahedron Asymmetry; vol. 18; nb. 14; (2007); p. 1643 - 1647 View in Reaxys With sodium isopropylate, lithium chloride in isopropyl alcohol, Time= 2h, T= 20 °C , Title compound not separated from byproducts. Ahlford, Katrin; Zaitsev, Alexey B.; Ekstroem, Jesper; Adolfsson, Hans; Synlett; nb. 16; (2007); p. 2541 - 2544 View in Reaxys With triphenylphosphine, [(η6-C6H6)Ru(μ-Cl)Cl]2 in isopropyl alcohol, Time= 1h, T= 100 °C , Title compound not separated from byproducts. Enthaler, Stephan; Hagemann, Bernhard; Bhor, Santosh; Anilkumar, Gopinathan; Tse, Man Kin; Bitterlich, Bianca; Junge, Kathrin; Erre, Giulia; Beller, Matthias; Advanced Synthesis and Catalysis; vol. 349; nb. 6; (2007); p. 853 - 860 View in Reaxys With PMHS, diethylzinc in toluene, Time= 16h, T= 20 °C , Title compound not separated from byproducts. Bandini, Marco; Melucci, Manuela; Piccinelli, Fabio; Sinisi, Riccardo; Tommasi, Simona; Umani-Ronchi, Achille; Chemical Communications; nb. 43; (2007); p. 4519 - 4521 View in Reaxys With sodium tetrahydroborate in tetrahydrofuran, Time= 1h, in air, Title compound not separated from byproducts. Eagon, Scott; Kim, Jinsoo; Yan, Katie; Haddenham, Dustin; Singaram, Bakthan; Tetrahedron Letters; vol. 48; nb. 51; (2007); p. 9025 - 9029 View in Reaxys With potassium tert-butylate, hydrogen, RuCl2-chiral BINAP-chiral diamine containing polymer complex in N,N-dimethyl-formamide, isopropyl alcohol, tert-butyl alcohol, Time= 24h, T= 20 °C , p= 7500.75Torr , Title compound not separated from byproducts. Takahashi, Miyuki; Haraguchi, Naoki; Itsuno, Shinichi; Tetrahedron Asymmetry; vol. 19; nb. 1; (2008); p. 60 - 66 View in Reaxys With sodium isopropylate, isopropyl alcohol, (pentamethylcyclopentadienyl)Rh(III) dichloride dimer, Time= 2h, T= 20 °C , Title compound not separated from byproducts. Wettergren, Jenny; Zaitsev, Alexey B.; Adolfsson, Hans; Advanced Synthesis and Catalysis; vol. 349; nb. 17-18; (2007); p. 2556 - 2562 View in Reaxys With dimethylsulfide borane complex, 1,1,1-tris{4-[4-(pyrrolidinsulfonyl)benzyloxy]phenyl}ethane in tetrahydrofuran, Time= 1h, Heating, Title compound not separated from byproducts. Li, Gao-Qiang; Yan, Ze-Yi; Niu, Yan-Ning; Wu, Lu-Yong; Wei, Hai-Long; Liang, Yong-Min; Tetrahedron Asymmetry; vol. 19; nb. 7; (2008); p. 816 - 821

149/258

2018-07-03 17:29:03

View in Reaxys With sodium formate, [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2 in water, Time= 2h, T= 20 °C , Title compound not separated from byproducts. Liu, Juntao; Zhou, Yougui; Wu, Yinuo; Li, Xingshu; Chan, Albert S.C.; Tetrahedron Asymmetry; vol. 19; nb. 7; (2008); p. 832 - 837 View in Reaxys With potassium tert-butylate, isopropyl alcohol, [Fe(CO)(NCMe){(R,R)-cyP2N2}][BF4]2, Time= 3.6h, T= 22 °C , Title compound not separated from byproducts. Sui-Seng, Christine; Freutel, Friederike; Lough, Alan J.; Morris, Robert H.; Angewandte Chemie - International Edition; vol. 47; nb. 5; (2008); p. 940 - 943 View in Reaxys With dimethylsulfide borane complex in tetrahydrofuran, Time= 1h, Heating, Title compound not separated from byproducts. Niu, Yan-Ning; Yan, Ze-Yi; Li, Gao-Qiang; Wei, Hai-Long; Gao, Guo-Lin; Wu, Lu-Yong; Liang, Yong-Min; Tetrahedron Asymmetry; vol. 19; nb. 8; (2008); p. 912 - 920 View in Reaxys With sodium formate, [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2 in water, T= 20 °C , Title compound not separated from byproducts. Liu, Juntao; Wu, Yinuo; Li, Xingshu; Chan, Albert S.C.; Journal of Organometallic Chemistry; vol. 693; nb. 12; (2008); p. 2177 - 2180 View in Reaxys With potassium hydroxide, hydrogen, Ru-PPh3/η-Al2O3 in isopropyl alcohol, Time= 3h, T= 40 °C , p= 37503.8Torr , Title compound not separated from byproducts. Tang, Bo; Xiong, Wei; Liu, De-Rong; Jia, Yun; Wang, Jin-Bo; Chen, Hua; Li, Xian-Jun; Tetrahedron Asymmetry; vol. 19; nb. 11; (2008); p. 1397 - 1401 View in Reaxys With Rhizopus arrhizus in ethanol, Time= 192h, T= 20 °C , Title compound not separated from byproducts. Salvi, Neeta A.; Chattopadhyay, Subrata; Tetrahedron Asymmetry; vol. 19; nb. 16; (2008); p. 1992 - 1997 View in Reaxys With diethoxymethylane, iron(II) acetate in tetrahydrofuran, Time= 32h, T= 20 °C , Title compound not separated from byproducts. Shaikh, Nadim S.; Enthaler, Stephan; Junge, Kathrin; Beller, Matthias; Angewandte Chemie - International Edition; vol. 47; nb. 13; (2008); p. 2497 - 2501 View in Reaxys With ethanol, Time= 24h, T= 30 °C , Microbiological reaction, optical yield given as percent ee Lavandera, Ivan; Oberdorfer, Gustav; Gross, Johannes; De Wildeman, Stefaan; Kroutil, Wolfgang; European Journal of Organic Chemistry; nb. 15; (2008); p. 2539 - 2543 View in Reaxys With dimethyl sulfide borane, (2S)-2-(anilinomethyl)pyrrolidine in tetrahydrofuran, Time= 2h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Hosoda, Naoya; Iogawa, Yoshihiro; Shimada, Yuichi; Asami, Masatoshi; Bulletin of the Chemical Society of Japan; vol. 81; nb. 2; (2008); p. 274 - 277 View in Reaxys With (2S)-N-[(1R,2S)-2,3-dihydro-2-hydroxy-1H-inden-1-yl]pyrrolidine-2-carboxamide, dichloro(p-cymene)ruthenium(II) dimer, sodium formate in water, Time= 20h, T= 30 °C , Inert atmosphere, optical yield given as percent ee Zeror, Saoussen; Collin, Jacqueline; Fiaud, Jean-Claude; Zouioueche, Louisa Aribi; Advanced Synthesis and Catalysis; vol. 350; nb. 1; (2008); p. 197 - 204

150/258

2018-07-03 17:29:03

View in Reaxys With (S)-(pyrrolidin-2-yl)diphenylmethanamine, dimethylsulfide borane complex in toluene, Time= 8h, T= -78 °C , optical yield given as percent ee, enantioselective reaction Luis Olivares-Romero; Juaristi, Eusebio; Tetrahedron; vol. 64; nb. 42; (2008); p. 9992 - 9998 View in Reaxys Stage 1: With polymethylhydrosiloxane, (S)-(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine) in toluene, Time= 24h, T= 20 °C , Inert atmosphere Stage 2: With tetrabutyl ammonium fluoride, water in tetrahydrofuran, diethyl ether, Time= 0.5h, optical yield given as percent ee, enantioselective reaction Kantam, M. Lakshmi; Laha, Soumi; Yadav, Jagjit; Likhar, Pravin R.; Sreedhar, Bojja; Jha, Shailendra; Bhargava, Suresh; Udayakiran; Jagadeesh; Organic Letters; vol. 10; nb. 14; (2008); p. 2979 - 2982 View in Reaxys With isopropyl alcohol, NADPH, Time= 24h, T= 30 °C , pH= 7.5, Microbiological reaction, aq. buffer, optical yield given as percent ee Lavandera, Ivan; Kern, Alexander; Resch, Verena; Ferreira-Silva, Bianca; Glieder, Anton; Fabian, Walter M. F.; De Wildeman, Stefaan; Kroutil, Wolfgang; Organic Letters; vol. 10; nb. 11; (2008); p. 2155 - 2158 View in Reaxys With lithium hydroxide, hydrogen, triphenylphosphine, iridium, (8R,9R)-9-amino(9-deoxy)epicinchonin in methanol, Time= 10h, T= 40 °C , p= 45004.5Torr , optical yield given as percent ee, enantioselective reaction Jiang, He-Yan; Yang, Chao-Fen; Li, Chun; Fu, Hai-Yan; Chen, Hua; Li, Rui-Xiang; Li, Xian-Jun; Angewandte Chemie International Edition; vol. 47; nb. 48; (2008); p. 9240 - 9244 View in Reaxys With lithium hydroxide, (S)-quinolin-4-yl((1S,2S,4S,5R)-5-vinylquinuclidin-2-yl)methanamine, hydrogen, triphenylphosphine, iridium in methanol, Time= 3h, T= 30 °C , p= 45004.5Torr , optical yield given as percent ee, enantioselective reaction Jiang, He-Yan; Yang, Chao-Fen; Li, Chun; Fu, Hai-Yan; Chen, Hua; Li, Rui-Xiang; Li, Xian-Jun; Angewandte Chemie International Edition; vol. 47; nb. 48; (2008); p. 9240 - 9244 View in Reaxys Stage 1: With aluminum(III) nitrate nonahydrate, sodium hydroxide, polymethylhydrosiloxane, copper(II) nitrate trihydrate, sodium carbonate, (S)-(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine) in toluene, T= 20 °C , Inert atmosphere Stage 2: With tetrabutyl ammonium fluoride in tetrahydrofuran, diethyl ether, Time= 0.5h Kantam, M. Lakshmi; Laha, Soumi; Yadav, Jagjit; Likhar, Pravin R.; Sreedhar; Jha, Shailendra; Bhargava, Suresh; Udayakiran; Jagadeesh; Organic Letters; vol. 10; nb. 19; (2008); p. 4391 - 4391 View in Reaxys Stage 1: With (4R,5R)-2-phenyl-1,3,2-dioxaborolane-4,5-dicarboxylic acid in tetrahydrofuran, Time= 0.25h, Cooling with ice Stage 2: With sodium tetrahydroborate in tetrahydrofuran, Time= 2h, optical yield given as percent ee Eagon, Scott; Kim, Jinsoo; Singaram, Bakthan; Synthesis; nb. 23; (2008); p. 3874 - 3876; Art.No: Z18008SS View in Reaxys With C64H60Cl2N2O2P2Ru, potassium tert-butylate, hydrogen in isopropyl alcohol, Time= 8h, T= 25 - 28 °C , p= 30402Torr , optical yield given as percent ee, enantioselective reaction Yuan, Wei-Cheng; Cun, Lin-Feng; Mi, Ai-Qiao; Jiang, Yao-Zhong; Gong, Liu-Zhu; Tetrahedron; vol. 65; nb. 21; (2009); p. 4130 - 4141 View in Reaxys With sodium hexaflorophosphate, bis(1,5-cyclooctadiene)diiridium(I) dichloride, (ηS,ηS)-1,1'-bis[η-(dimethylamino)benzyl](R,R)-2,2'-bis(dicyclohexylphosphino)ferrocene, isopropyl alcohol, sodium t-butanolate, Time= 14h, T= 40 °C , Inert atmosphere Lundgren, Rylan J.; Stradiotto, Mark; Chemistry - A European Journal; vol. 14; nb. 33; (2008); p. 10388 - 10395 View in Reaxys

151/258

2018-07-03 17:29:03

Stage 1: With polymethylhydrosiloxane, copper(II) ferrite, (S)-(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine) in toluene, Time= 30h, T= 20 °C Stage 2: With tetrabutyl ammonium fluoride, water in tetrahydrofuran, diethyl ether, toluene, Time= 0.5h, optical yield given as percent ee, enantioselective reaction Kantam, M. Lakshmi; Yadav, Jagjit; Laha, Soumi; Srinivas, Pottabathula; Sreedhar, Bojja; Figueras; Journal of Organic Chemistry; vol. 74; nb. 12; (2009); p. 4608 - 4611 View in Reaxys Stage 1: With polymethylhydrosiloxane, diethylzinc, (2R,3R,12R,13R,22R,23R)-1,4,11,14,21,24-hexaaza-(2,3:12,13:22,23)tributano-(6,9:16,19:26,29)-trietheno-(1H,2H,3H,4H,5H,10H,11H,12H,13H,14H,15H,20H,21H,22H,23H,24H,25H,30H)-octadecahydro-(30)-annulene in hexane, toluene, Time= 24h, T= 20 °C , Inert atmosphere Stage 2: With sodium hydroxide in methanol, hexane, toluene, Time= 1h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Gajewy, Jadwiga; Kwit, Marcin; Gawronski, Jacek; Advanced Synthesis and Catalysis; vol. 351; nb. 7-8; (2009); p. 1055 1063 View in Reaxys With [(η6-C6H6)Ru(μ-Cl)Cl]2, C22H32N4O4S2, isopropyl alcohol, potassium hydroxide, Time= 5h, T= 40 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Montalvo-Gonzalez, Ruben; Chavez, Daniel; Aguirre, Gerardo; Parra-Hake, Miguel; Somanathan, Ratnasamy; Synthetic Communications; vol. 39; nb. 15; (2009); p. 2737 - 2746 View in Reaxys With trans-(R,R)-[Fe(NCMe)(CO)(diph-ethP2N2)][BF4]2, potassium tert-butylate, isopropyl alcohol, Time= 0.5h, T= 20 °C , Inert atmosphere, optical yield given as percent ee Meyer, Nils; Lough, Alan J.; Morris, Robert H.; Chemistry - A European Journal; vol. 15; nb. 22; (2009); p. 5605 - 5610 View in Reaxys With iridium(III) chloride, (S,S)-naphthalene-2-sulfonic acid (1,2-diphenyl-2-propylaminoethyl)-amide, hydrogen, sodium hydroxide in methanol, Time= 24h, T= 40 °C , p= 37503.8Torr , optical yield given as percent ee, enantioselective reaction Martins, Jose E.D.; Wills, Martin; Tetrahedron; vol. 65; nb. 29-30; (2009); p. 5782 - 5786 View in Reaxys Stage 1: With phenylsilane, copper diacetate, (S)-4-phenyl-4,5-dihydro-3H-dinaphtho<2,1-c;1',2'-e>phosphepine in toluene, Time= 5h, T= -20 °C , Inert atmosphere Stage 2: With methanol, tetrabutyl ammonium fluoride in tetrahydrofuran, Time= 2h, optical yield given as percent ee, enantioselective reaction Junge, Kathrin; Wendt, Bianca; Addis, Daniele; Zhou, Shaolin; Das, Shoubhik; Beller, Matthias; Chemistry - A European Journal; vol. 16; nb. 1; (2010); p. 68 - 73 View in Reaxys With [RhCl2(p-cymene)]2, potassium hydroxide in isopropyl alcohol, T= 20 °C , Inert atmosphere, enantioselective reaction Michalek, Florian; Lagunas, Anna; Jimeno, Ciril; Pericas, Miquel A.; Journal of Materials Chemistry; vol. 18; nb. 39; (2008); p. 4692 - 4697 View in Reaxys With trans-[Ru((R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl)(H)(η1-BH4)((R,R)-1,2-diphenylethylenediamine)], potassium tert-butylate, hydrogen in isopropyl alcohol, T= 30 - 32 °C , p= 3040.2Torr , optical yield given as percent ee, enantioselective reaction Sandoval, Christian A.; Shi, Qixun; Liu, Shasha; Noyori, Ryoji; Chemistry - An Asian Journal; vol. 4; nb. 8; (2009); p. 1221 - 1224 View in Reaxys With formate dehydrogenase, recombinant diketoreductase, NAD, sodium formate in ethanol, Time= 18h, T= 20 °C , pH= 6, aq. potassium phosphate buffer, Enzymatic reaction, optical yield given as percent ee

152/258

2018-07-03 17:29:03

Wu, Xuri; Wang, Yuchen; Ju, Jianming; Chen, Chen; Liu, Nan; Chen, Yijun; Tetrahedron Asymmetry; vol. 20; nb. 21; (2009); p. 2504 - 2509 View in Reaxys Stage 1: With copper (II)-fluoride, 1,2,4,5-tetra[(4'S)-isopropyloxazolin-2'-yl]benzene, diphenylsilane in dichloromethane, Time= 12h, T= -5 °C , Air atmosphere Stage 2: With hydrogenchloride in methanol, dichloromethane, water, optical yield given as percent ee, enantioselective reaction Li, Wei Jie; Qiu, Sheng Xiang; Advanced Synthesis and Catalysis; vol. 352; nb. 7; (2010); p. 1119 - 1122 View in Reaxys With (C(CH3)3)2C7H6O2N2BHC8H14, boron trifluoride diethyl etherate in dichloromethane, Time= 16h, T= -90 °C , optical yield given as percent ee Lindsay, David M.; McArthur, David; Chemical Communications; vol. 46; nb. 14; (2010); p. 2474 - 2476 View in Reaxys With C23H36IrN4 (1+)*F6P(1-), isopropyl alcohol, potassium hydroxide, Time= 15h, T= 82 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Diez, Claus; Nagel, Ulrich; Applied Organometallic Chemistry; vol. 24; nb. 7; (2010); p. 509 - 516 View in Reaxys With C40H58Cl2FeN4O6P2, potassium tert-butylate, isopropyl alcohol, Time= 6h, T= 22 - 24 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Naik, Anu; Maji, Tapan; Reiser, Oliver; Chemical Communications; vol. 46; nb. 25; (2010); p. 4475 - 4477 View in Reaxys With hydrogen, potassium hydroxide, 9-amino-9-deoxyepicinchonine in isopropyl alcohol, Time= 5h, T= 40 °C , p= 45004.5Torr , Autoclave, optical yield given as percent ee, enantioselective reaction Jiang, He-yan; Chen, Hua; Li, Rui-xiang; Catalysis Communications; vol. 11; nb. 7; (2010); p. 584 - 587 View in Reaxys With borane-dimethyl sulfide complex, C12H22BNO in tetrahydrofuran, Time= 1h, T= 20 °C , Inert atmosphere, optical yield given as percent ee Yang, Te-Fang; Shen, Chien-Hung; Hsu, Chi-Tung; Chen, Li-Hsun; Chuang, Chih-Hsiang; Tetrahedron; vol. 66; nb. 45; (2010); p. 8734 - 8738 View in Reaxys With C68H78Cl2N2O6P2Ru, hydrogen, potassium hydroxide in isopropyl alcohol, Time= 12h, T= 20 °C , p= 22502.3Torr , Autoclave, optical yield given as percent ee, enantioselective reaction Ma, Meng Lin; Peng, Zong Hai; Guo, Yu; Chen, Li; Chen, Hua; Li, Xian Jun; Chinese Chemical Letters; vol. 21; nb. 5; (2010); p. 576 - 579 View in Reaxys With potassium tert-butylate, hydrogen, copper diacetate, 4-(4-trifluoromethyl-phenyl)-4,5-dihydro-3H-4-phospha-cyclohepta[2,1-a;3,4-a']dinaphthalene in isopropyl alcohol, Time= 16h, T= 10 °C , p= 37503.8Torr , Inert atmosphere, Autoclave, optical yield given as percent ee, enantioselective reaction Junge, Kathrin; Wendt, Bianca; Addis, Daniele; Zhou, Shaolin; Das, Shoubhik; Fleischer, Steffen; Beller, Matthias; Chemistry - A European Journal; vol. 17; nb. 1; (2011); p. 101 - 105 View in Reaxys With iridium(III) chloride hydrate, C24H28N2O2S, hydrogen, sodium hydroxide in methanol, Time= 24h, T= 40 °C , p= 37503.8Torr , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Martins, Jose E.D.; Morris, David J.; Wills, Martin; Tetrahedron Letters; vol. 50; nb. 6; (2009); p. 688 - 692 View in Reaxys With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer, N-((1R,2R)-2-aminocyclohexyl)(phenyl)methanesulfonamide, sodium formate in water, Time= 4h, T= 40 °C , optical yield given as percent ee, enantioselective reaction

153/258

2018-07-03 17:29:03

Cortez, Norma A.; Aguirre, Gerardo; Parra-Hake, Miguel; Somanathan, Ratnasamy; Arita, Amy J.; Cooksy, Andrew L.; De Parrodi, Cecilia Anaya; Huelgas, Gabriela; Synthetic Communications; vol. 41; nb. 1; (2011); p. 73 - 84 View in Reaxys With [RhCl2(p-cymene)]2, 5-[(2S,4R)-4-(tert-butyldiphenylsilyloxy)pyrrolidin-2-yl]-1H-1,2,3-triazole, potassium hydroxide in isopropyl alcohol, Time= 4h, T= 20 °C , Inert atmosphere, optical yield given as percent ee Cambeiro, Xacobe C.; Pericas, Miquel A.; Advanced Synthesis and Catalysis; vol. 353; nb. 1; (2011); p. 113 - 124 View in Reaxys With (2-((2,4-dimethyl-5-phenylimidazo[1,5-b]pyridazin-7-yl)amido)propan-1-ol)(1,5-cyclooctadiene)iridium(I) hemitetrahydrofuran complex, potassium tert-butylate, hydrogen in tetrahydrofuran, Time= 48h, T= 20 °C , p= 15.0015Torr , Autoclave, optical yield given as percent ee, enantioselective reaction Irrgang, Torsten; Friedrich, Denise; Kempe, Rhett; Angewandte Chemie - International Edition; vol. 50; nb. 9; (2011); p. 2183 - 2186 View in Reaxys 4.3. General procedure for the transfer hydrogenation of aromatic ketones General procedure: A mixture of [RuCl2(p-cymene)]2 (1.5 mg, 0.0025 mmol) and (S)-4a (3.0 mg, 0.02 mmol) in 2 mL of 2propanol was stirred at 80 °C for 30 min under argon atmosphere. After cooling to room temperature, 2-propanol (15 mL), KOH (0.6 mL, 0.1 M in 2-propanol), acetophenone (0.5 mmol, dissolved in 5 mL of 2-propanol) were added. The resulting solution was stirred at -10 °C, and the reaction was monitored by GC or HPLC. The mixture was neutralized with dilute HCl and 2propanol was removed under reduced pressure. The residue was diluted with ethyl acetate (25 mL) and the organic solution was washed with brine (3 .x. 20 mL) and dried over anhydrous MgSO4. After evaporation of the solvent, the residue was subjected to short column chromatography on silica gel (hexane/ethyl acetate as eluent) for ee and conversion determination. With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, {2-[(S)-1-aminoethyl]phenyl}methanol, isopropyl alcohol, potassium hydroxide, Time= 3h, T= -10 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Han, Mei-Ling; Hu, Xiang-Ping; Huang, Jia-Di; Chen, Li-Gong; Zheng, Zhuo; Tetrahedron Asymmetry; vol. 22; nb. 2; (2011); p. 222 - 225 View in Reaxys 3.2. General procedure for the transfer hydrogenation of ketones General procedure: a solution of the ruthenium complexesμ-(2R)-2-[benzyl{(2-(diphenylphosphanyl)oxy)ethyl)}amino]butyldiphenylphosphinito-bis[dichloro(η6-p-isopropyltoluene)ruthenium(II)], 3 and μ-(2R)-2-[benzyl{(2-((dicyclohexylphosphanyl)oxy)ethyl)}amino]butyldicyclohexylphosphinito-bis[dichloro(η6-p-isopropyltoluene)ruthenium(II)], 4 (0.005 mmol), KOH (0.025 mmol) and the corresponding ketone (0.5 mmol) in degassed iso-PrOH (5 mL) was refluxed up to the reaction completed. After this time a sample of the reaction mixture is taken off, diluted with acetone and analyzed immediately by GC, conversions obtained are related to the residual unreacted ketone. With μ-(2R)-2-[benzyl{(2-((dicyclohexylphosphanyl)oxy)ethyl)}amino]butyldicyclohexylphosphinito-bis[dichloro(η6-p-isopropyltoluene)ruthenium(II)], sodium hydroxide in isopropyl alcohol, Time= 23h, T= 82 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Aydemir, Murat; Meric, Nermin; Baysal, Akin; Turgut, Yilmaz; Kayan, Cezmi; Seker, Sevil; Togrul, Mahmut; Guemguem, Bahattin; Journal of Organometallic Chemistry; vol. 696; nb. 8; (2011); p. 1541 - 1546 View in Reaxys The Typical Procedure for Asymmetric Hydrogenation (R)-C4-Tunephos (3.6 mg, 0.006 mmol) and Pd(CF3CO2)2 (1.7 mg, 0.005 mmol) were placed in a dried Schlenk tube under nitrogen atmosphere, and degassed anhydrous acetone was added. The mixture was stirred at room temperature for 1 h. The solvent was removed under vacuum to give the catalyst. To this was added dry TFE (2 mL) followed by ketone and additive under a hydrogen atmosphere. Then the mixture was stirred at room temperature. After confirmation of consumption of substrate by TLC, GC or 1H NMR, and then the hydrogen gas was slowly released. The conversion was directly determined by 1H NMR spectroscopy or GC. The enantiomeric excess was determined by HPLC after purification on silica gel using petroleum ether and EtOAc or directly determined by GC. With (R)-C4-TunePhos, palladium(II) trifluoroacetate, hydrogen, salicylic acid in 2,2,2-trifluoroethanol, T= 20 °C , p= 760.051Torr , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Zhou, Xiao-Yu; Wang, Duo-Sheng; Bao, Ming; Zhou, Yong-Gui; Tetrahedron Letters; vol. 52; nb. 22; (2011); p. 2826 - 2829

154/258

2018-07-03 17:29:03

View in Reaxys With chloro(1,5-cyclooctadiene)rhodium(I) dimer, C7H7O3S(1-)*C9H14N3O(1+), potassium tert-butylate, potassium hydroxide in isopropyl alcohol, Time= 20h, T= 80 °C , Inert atmosphere Aupoix, Audrey; Bournaud, Chloee; Vo-Thanh, Giang; European Journal of Organic Chemistry; nb. 15; (2011); p. 2772 2776 View in Reaxys With water, sodium formate, sodium dodecyl-sulfate, Time= 96h, T= 39.84 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Weng, Zhihuan; Muratsugu, Satoshi; Ishiguro, Nozomu; Ohkoshi, Shin-Ichi; Tada, Mizuki; Dalton Transactions; vol. 40; nb. 10; (2011); p. 2338 - 2347 View in Reaxys With [RhCl2(p-cymene)]2, C2F3O2 (1-)*C2HF3O2*C19H25N4O3S(1+), sodium formate in water, Time= 4h, T= 40 °C , Inert atmosphere, optical yield given as percent ee Zhou, Zhongqiang; Ma, Qiong; Sun, Yong; Zhang, Aiqing; Li, Lin; Heteroatom Chemistry; vol. 21; nb. 7; (2010); p. 505 514 View in Reaxys With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer, (R,R)-N-(4'-nitrophenylsulfonyl)-1,2-diaminocyclohexane, sodium formate in water, Time= 0.3h, T= 40 °C , optical yield given as percent ee, enantioselective reaction Barron-Jaime, Angelica; Narvaez-Garayzar, Oscar F.; Gonzalez, Jorge; Ibarra-Galvan, Valentin; Aguirre, Gerardo; Parra-Hake, Miguel; Chavez, Daniel; Somanathan, Ratnasamy; Chirality; vol. 23; nb. 2; (2011); p. 178 - 184 View in Reaxys Reaction Steps: 2 2: C13H14N2*C18H14O8 / water; acetonitrile / 20 °C / Resolution of racemate With C13H14N2*C18H14O8 in water, acetonitrile Kodama, Koichi; Sekine, Eriko; Hirose, Takuji; Chemistry - A European Journal; vol. 17; nb. 41; (2011); p. 11527 - 11534 View in Reaxys 3.3. Microbial reduction of substrates General procedure: The substrates (each 100 mg) in EtOH (1 mL) were added to the culture and shaken for the periods shown in the Tables. Substrate and organism controls were also run simultaneously in each case. At the end of fermentation, the mycelial mass was filtered from the culture medium. The filtrate was extracted with chloroform (2 .x. 50 mL), washed with H2O (2 .x. 20 mL) and dried. Removal of the solvent gave a residue which on preparative thin-layer chromatography (silica gel, EtOAc/ hexane) furnished the respective product alcohols. The spectral and chiroptical data of compounds 1b, 2b, 4b, 7b and 9b matched those reported by us previously.9c With water in ethanol, Time= 168h, modified Czepak Dox medium, optical yield given as percent ee, enantioselective reaction Salvi, Neeta A.; Chattopadhyay, Subrata; Tetrahedron Asymmetry; vol. 22; nb. 14-15; (2011); p. 1512 - 1515 View in Reaxys With dimethylsulfide borane complex, C72H66N6O9 in toluene, Time= 2.5h, T= 30 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Wu, Xiang-Fei; Min, Chang; Nyamzundui, Enkhtsetseg; Zhou, Hai-Bing; Dong, Chune; Tetrahedron Asymmetry; vol. 22; nb. 16-17; (2011); p. 1640 - 1643 View in Reaxys With dimethylamine borane, [(R)-xylylBINAP][(R,R)-DPEN]RuCl2, potassium tert-butylate in tetrahydrofuran, Time= 24h, T= 21 °C , Inert atmosphere, optical yield given as percent ee Nixon, Tracy D.; Whittlesey, Michael K.; Williams, Jonathan M.J.; Tetrahedron Letters; vol. 52; nb. 49; (2011); p. 6652 6654 View in Reaxys

155/258

2018-07-03 17:29:03

With [(η4-cyclooctadiene)IrCl(PPh3)], potassium hydroxide in isopropyl alcohol, Time= 5h, T= 60 °C , Inert atmosphere, optical yield given as percent ee Yu, Shen Luan; Li, Yan Yun; Dong, Zhen Rong; Zhang, Juan Ni; Li, Qi; Gao, Jing Xing; Chinese Chemical Letters; vol. 22; nb. 11; (2011); p. 1269 - 1272 View in Reaxys With bis(1,5-cyclooctadiene)diiridium(I) dichloride, potassium hydroxide in isopropyl alcohol, Time= 5h, T= 60 °C , Inert atmosphere, optical yield given as percent ee Yu, Shen Luan; Li, Yan Yun; Dong, Zhen Rong; Zhang, Juan Ni; Li, Qi; Gao, Jing Xing; Chinese Chemical Letters; vol. 22; nb. 11; (2011); p. 1269 - 1272 View in Reaxys With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer, (S)-N-[(1S,2S)-2-(4-methylphenylsulfonamido)-1,2-diphenylethyl]pyrrolidine-2-carboxamide, sodium formate in water, Time= 24h, T= 60 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Manville, Charles V.; Docherty, Gordon; Padda, Ranbir; Wills, Martin; European Journal of Organic Chemistry; nb. 34; (2011); p. 6893 - 6901 View in Reaxys With (2S)-N-{(1R,2R)-2-[(S)-pyrrolidine-2-carboxamido]-1,2-diphenylethyl}pyrrolidine-2-carboxamide, [ruthenium(II)(η6-1methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, sodium formate in water, Time= 24h, T= 60 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Manville, Charles V.; Docherty, Gordon; Padda, Ranbir; Wills, Martin; European Journal of Organic Chemistry; nb. 34; (2011); p. 6893 - 6901 View in Reaxys With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer, lithium formate, L-prolinamide in water, Time= 18h, T= 35 °C , optical yield given as percent ee, enantioselective reaction Ahlford, Katrin; Adolfsson, Hans; Catalysis Communications; vol. 12; nb. 12; (2011); p. 1118 - 1121 View in Reaxys Reaction Steps: 2 1: sodium tetrahydroborate 2: Br(1-)*C75H107Cl2Mn2N8O4 (1+); potassium bromide / dichloromethane; water / 0.17 h / 20 °C With sodium tetrahydroborate, Br(1-)*C75H107Cl2Mn2N8O4 (1+), potassium bromide in dichloromethane, water Li, Chengyong; Zhao, Jiangfeng; Tan, Rong; Peng, Zhigang; Luo, Rongchang; Peng, Ming; Yin, Donghong; Catalysis Communications; vol. 15; nb. 1; (2011); p. 27 - 31 View in Reaxys With [Rh(tert-butyl 2-O-diphenylphosphinite-3,4,6-tri-O-benzyl-1-thio-η-D-glucopyranoside)(norbornadiene)]OTf, diphenylsilane in tetrahydrofuran, Time= 24h, T= 25 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Khiar, Noureddine; Leal, Manuel Pernia; Navas, Raquel; Moya, Juan Francisco; Perez, Maria Victoria Garcia; Fernandez, Inmaculada; Organic and Biomolecular Chemistry; vol. 10; nb. 2; (2012); p. 355 - 360 View in Reaxys Stage 1: With diethylzinc, 2,6-bis((R)-4-phenyl-4,5-dihydrooxazol-2-yl)pyridine in tetrahydrofuran, toluene, Time= 20h, T= 20 °C , Inert atmosphere Stage 2: With sodium hydroxide in tetrahydrofuran, methanol, diethyl ether, toluene, Time= 0.5h, Inert atmosphere, optical yield given as percent ee, enantioselective reaction Junge, Kathrin; Moeller, Konstanze; Wendt, Bianca; Das, Shoubhik; Goerdes, Dirk; Thurow, Kerstin; Beller, Matthias; Chemistry - An Asian Journal; vol. 7; nb. 2; (2012); p. 314 - 320 View in Reaxys Stage 1: With silver tetrafluoroborate, diethoxymethylane, C29H37ClIrN3O2 in 2-methyltetrahydrofuran, Time= 20h, T= 20 °C Stage 2: With methanol, potassium carbonate in 2-methyltetrahydrofuran, Time= 2h, T= 20 °C , optical yield given as percent ee, enantioselective reaction

156/258

2018-07-03 17:29:03

Kawabata, Shun; Tokura, Hiromu; Chiyojima, Hiroyuki; Okamoto, Masaki; Sakaguchi, Satoshi; Advanced Synthesis and Catalysis; vol. 354; nb. 5; (2012); p. 807 - 812 View in Reaxys With bis(triphenylphosphine)nickel(II) chloride, C36H37N2O2P, potassium hydroxide in isopropyl alcohol, Time= 21h, T= 70 °C , enantioselective reaction Dong, Zhen Rong; Li, Yan Yun; Yu, Shen Luan; Sun, Guo Song; Gao, Jing Xing; Chinese Chemical Letters; vol. 23; nb. 5; (2012); p. 533 - 536 View in Reaxys Reaction Steps: 2 1: sodium tetrahydroborate / ethanol / Inert atmosphere 2: bis(1,5-cyclooctadiene)diiridium(I) dichloride; cetyltrimethylammonim bromide; acetone; potassium hydroxide; N,N'-bis[o(diphenylphosphino)benzylidene]-(1S,2S)-diaiminocyclohexane / water / 16 h / 28 °C / Resolution of racemate; Inert atmosphere With sodium tetrahydroborate, bis(1,5-cyclooctadiene)diiridium(I) dichloride, cetyltrimethylammonim bromide, acetone, potassium hydroxide, N,N'-bis[o-(diphenylphosphino)benzylidene]-(1S,2S)-diaiminocyclohexane in ethanol, water Zhang, Juanni; Yang, Xiangren; Zhou, Han; Li, Yanyun; Dong, Zhenrong; Gao, Jingxing; Green Chemistry; vol. 14; nb. 5; (2012); p. 1289 - 1292 View in Reaxys With bis(triphenylphosphine)carbonyliridium(I) chloride, (R)-N,N'-bis[2-(piperidin-1-yl)benzylidene]propane-1,2-diamine, potassium hydroxide in isopropyl alcohol, Time= 10h, T= 75 °C , optical yield given as percent ee, enantioselective reaction Yu, Shen Luan; Li, Yan Yun; Dong, Zhen Rong; Gao, Jing Xing; Chinese Chemical Letters; vol. 23; nb. 4; (2012); p. 395 398 View in Reaxys With bis(triphenylphosphine)carbonyliridium(I) chloride, (S)-N-[2-(piperidin-1-yl)benzylidene]-3-{[2-(piperidin-1-yl)benzylidene]amino}-alanine sodium salt, potassium hydroxide in isopropyl alcohol, Time= 10h, T= 75 °C , optical yield given as percent ee, enantioselective reaction Yu, Shen Luan; Li, Yan Yun; Dong, Zhen Rong; Gao, Jing Xing; Chinese Chemical Letters; vol. 23; nb. 4; (2012); p. 395 398 View in Reaxys With (S)-(+)-1-(5-phenyl-4,5-dihydro-1,3-oxazol-2-yl)isoquinoline, trichlorosilane in chloroform, Time= 24h, T= -20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Malkov, Andrei V.; Stewart-Liddon, Angus J. P.; McGeoch, Grant D.; Ramirez-Lopez, Pedro; Kocovsky, Pavel; Organic and Biomolecular Chemistry; vol. 10; nb. 25; (2012); p. 4864 - 4877 View in Reaxys With chlorobis(cyclooctene)-iridium(I) dimer, (S)-N-(2-(tert-butylsulfinyl)benzyl)-1-(pyridin-2-yl)methanamine, potassium tertbutylate, isopropyl alcohol in dichloromethane, Time= 3h, T= 20 °C , optical yield given as percent ee, stereoselective reaction Tang, Lei; Wang, Qiwei; Wang, Juanjuan; Lin, Zechao; Wang, Xiaobei; Cun, Linfeng; Yuan, Weicheng; Zhu, Jin; Liao, Jian; Deng, Jingen; Tetrahedron Letters; vol. 53; nb. 30; (2012); p. 3839 - 3842 View in Reaxys With diethyl zinc, diphenylsilane, (2R,3R,12R,13R,22R,23R)-1,4,11,14,21,24-hexaaza-(2,3:12,13:22,23)-tributano-(6,9:16,19:26,29)-trietheno-(1H,2H,3H,4H,5H,10H,11H,12H,13H,14H,15H,20H,21H,22H,23H,24H,25H,30H)-octadecahydro-(30)-annulene in hexane, toluene, Time= 24h, T= 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Gajewy, Jadwiga; Gawronski, Jacek; Kwit, Marcin; Monatshefte fur Chemie; vol. 143; nb. 7; (2012); p. 1045 - 1054 View in Reaxys 4.2. Typical procedure for asymmetric hydrogenation of aromatic ketones General procedure: To a 60 mL stainless autoclave with a glass liner and magnetic stirrer were added PEG-400, H2O, RuCl2(TPPTS)2, (S,S)-DPENDS, KOH, and reactant. Hydrogen was introduced to the desired pressure after the reaction mixture had been purged with H2 five times. The products were extracted by n-hexane and analyzed by GC-960 with a FID detector and η-DEX.(TM).120 capillary column (30 m .x. 0.25 mm, 0.25 μm film) at 115 °C. The enantiomeric excess (ee value) was calculated from the equation: ee (percent) = 100 .x. (R - S)/(R + S).

157/258

2018-07-03 17:29:03

With (S,S)-DPENDS, C36H24Cl2O18P2RuS6 (6-)*6Na(1+), hydrogen, potassium hydroxide in water, Time= 3h, T= 30 °C , p= 37503.8Torr , Autoclave, optical yield given as percent ee, enantioselective reaction Qin, Ruixiang; Wang, Jinbo; Xiong, Wei; Chen, Hua; Feng, Jian; Liu, Derong; Tetrahedron Asymmetry; vol. 23; nb. 11-12; (2012); p. 834 - 837 View in Reaxys 4.1.7 General procedure for ketones reduction using catalysts 5–7 General procedure: To a ketone (2.4 mmol) placed in a vial 1 mL of CH3CN solution of the preformed ruthenium catalyst (24 μmol) and formic acid/triethylamine azeotropic mixture (1 mL) were added. The mixture was then stirred at room temperature and the progress of the reaction was monitored by TLC until the specified conversion was achieved. After evaporation of the solvents, 4 mL of CH2Cl2 and 1.5 mL of 10percent aqueous HCl solution were added to the residue. The layers were separated and the water layer was extracted twice with 2 mL of CH2Cl2. The combined organic layers were dried over Na2SO4 and the solvent was evaporated in vacuo. The residual oil was purified by column chromatography on silica gel using chloroform (dried over CaCl2) as eluent to afford the appropriate alcohol. The enantiomeric excess was determined by GC analysis using a Supelco cyclodextrin η-DEX 120 capillary column (20 m × 0.25 mm ID and 0.25 μm film thickness). The results of the reduction are summarized in Table 1. With formic acid, C23H32ClN2O2RuS, triethylamine in acetonitrile, Time= 480h, T= 20 °C , enantioselective reaction Roszkowski, Piotr; Maurin, Jan K.; Czarnocki, Zbigniew; Tetrahedron Asymmetry; vol. 23; nb. 14; (2012); p. 1106 - 1110 View in Reaxys 4.1.7 General procedure for ketones reduction using catalysts 5–7 General procedure: To a ketone (2.4 mmol) placed in a vial 1 mL of CH3CN solution of the preformed ruthenium catalyst (24 μmol) and formic acid/triethylamine azeotropic mixture (1 mL) were added. The mixture was then stirred at room temperature and the progress of the reaction was monitored by TLC until the specified conversion was achieved. After evaporation of the solvents, 4 mL of CH2Cl2 and 1.5 mL of 10percent aqueous HCl solution were added to the residue. The layers were separated and the water layer was extracted twice with 2 mL of CH2Cl2. The combined organic layers were dried over Na2SO4 and the solvent was evaporated in vacuo. The residual oil was purified by column chromatography on silica gel using chloroform (dried over CaCl2) as eluent to afford the appropriate alcohol. The enantiomeric excess was determined by GC analysis using a Supelco cyclodextrin η-DEX 120 capillary column (20 m × 0.25 mm ID and 0.25 μm film thickness). The results of the reduction are summarized in Table 1. With formic acid, C23H32ClN2O2RuS, triethylamine in acetonitrile, Time= 48h, T= 20 °C , enantioselective reaction Roszkowski, Piotr; Maurin, Jan K.; Czarnocki, Zbigniew; Tetrahedron Asymmetry; vol. 23; nb. 14; (2012); p. 1106 - 1110 View in Reaxys With sodium isopropylate in methanol, isopropyl alcohol, Time= 24h, T= 25 °C , Inert atmosphere, stereoselective reaction Babin, Mathieu; Clement, Roxanne; Gagnon, Jonathan; Fontaine, Frederic-Georges; New Journal of Chemistry; vol. 36; nb. 8; (2012); p. 1548 - 1551 View in Reaxys With N-[(1R,2R)-1,2-diphenyl-2-(3-phenylpropylamino)ethyl]-4-methylbenzene sulfonamide ammonium chloride ruthenium, hydrogen in methanol, Time= 48h, T= 60 °C , p= 22502.3Torr , enantioselective reaction Jolley, Katherine E.; Prokes, Ivan; Morris, David J.; Wills, Martin; Zanotti-Gerosa, Antonio; Hancock, Fred; Dyke, Alan; Grainger, Damian M.; Medlock, Jonathan A.; Nedden, Hans G.; Le Paih, Jacques J. M.; Roseblade, Stephen J.; Seger, Andreas; Sivakumar, Vilvanathan; Advanced Synthesis and Catalysis; vol. 354; nb. 13; (2012); p. 2545 - 2555,11 View in Reaxys Jolley, Katherine E.; Zanotti-Gerosa, Antonio; Hancock, Fred; Dyke, Alan; Grainger, Damian M.; Medlock, Jonathan A.; Nedden, Hans G.; Le Paih, Jacques J. M.; Roseblade, Stephen J.; Seger, Andreas; Sivakumar, Vilvanathan; Prokes, Ivan; Morris, David J.; Wills, Martin; Advanced Synthesis and Catalysis; vol. 354; nb. 13; (2012); p. 2545 - 2555 View in Reaxys With borane-THF, C27H25NO2 in tetrahydrofuran, T= 20 °C , Inert atmosphere, Overall yield = 95 percent; Optical yield = 11 percent ee; enantioselective reaction Ran, De-Qiang; Shen, Tian-Hua; Zhou, Xiao-Cong; Ma, Chun-An; Song, Qing-Bao; Journal of the Chemical Society of Pakistan; vol. 35; nb. 1; (2013); p. 125 - 129 View in Reaxys

158/258

2018-07-03 17:29:03

General procedure for ketone reduction using catalysts 12–18 General procedure: To a ketone (2.4 mmol) placed in a vial, 1 mL of CH3CN solution of preformed ruthenium catalyst (24 lmol) and formic acid/triethylamine azeotropic mixture (1 mL) were added. The mixture was then stirred at room temperature and the progress of the reaction was monitored by TLC until the specified conversion was achieved. After evaporation of the solvents, 4 mL of CH2Cl2 and 1.5 mL of 10percent aqueous HCl solution were added to the residue. The layers were separated and the water layer was extracted twice with 2 mL of CH2Cl2. The combined organic layers were dried over Na2SO4 and the solvent was evaporated in vacuo. The oily residue was purified by column chromatography on silica gel using chloroform (dried over CaCl2) as eluent to afford the appropriate ketone. The enantiomeric excess was determined by GC analysis using a Supelco cyclodextrinb-DEX 120 capillary column (20 m 0.25 mm I.D. and 0.25 lm film thickness). With formic acid, C23H30ClN2O2RuS, triethylamine in acetonitrile, Time= 480h, T= 20 °C Roszkowski, Piotr; Maurin, Jan K.; Czarnocki, Zbigniew; Tetrahedron Asymmetry; vol. 24; nb. 11; (2013); p. 643 - 650 View in Reaxys General procedure for ketone reduction using catalysts 12–18 General procedure: To a ketone (2.4 mmol) placed in a vial, 1 mL of CH3CN solution of preformed ruthenium catalyst (24 lmol) and formic acid/triethylamine azeotropic mixture (1 mL) were added. The mixture was then stirred at room temperature and the progress of the reaction was monitored by TLC until the specified conversion was achieved. After evaporation of the solvents, 4 mL of CH2Cl2 and 1.5 mL of 10percent aqueous HCl solution were added to the residue. The layers were separated and the water layer was extracted twice with 2 mL of CH2Cl2. The combined organic layers were dried over Na2SO4 and the solvent was evaporated in vacuo. The oily residue was purified by column chromatography on silica gel using chloroform (dried over CaCl2) as eluent to afford the appropriate ketone. The enantiomeric excess was determined by GC analysis using a Supelco cyclodextrinb-DEX 120 capillary column (20 m 0.25 mm I.D. and 0.25 lm film thickness). With formic acid, C23H32ClN2O2RuS, triethylamine in acetonitrile, Time= 96h, T= 20 °C , Reagent/catalyst Roszkowski, Piotr; Maurin, Jan K.; Czarnocki, Zbigniew; Tetrahedron Asymmetry; vol. 24; nb. 11; (2013); p. 643 - 650 View in Reaxys 4.3 General procedure for the enantioselective reduction of ketones with borane-dimethyl sulfide in the presence of ̈-hydroxyamides 1–7 General procedure: A 25mL two-necked flask was charged with η-hydroxyamide 1–7 (0.05mmol, 10percent) in dry and fresh THF (3mL), equipped with a magnetic stirrer and a connection to the combined nitrogen/vacuum line and closed with a septum. The air in the flask was replaced by nitrogen. η-hydroxyamides 1–7 were dissolved in THF (3mL) with stirring and a solution of BH3·SMe2 (0.5mmol, 10M) complex was added at 0°C by a syringe. After the mixture was stirred for 1h at 65°C, the freshly distilled ketone (0.5mmol) in freshly dried THF (2mL) was added over a period of 1.5h by a syringe at the same temperature. The reaction mixture was kept stirring at the 65°C until the ketone was completely consumed. After stirring for a further 30min at rt, the reaction mixture was quenched by the addition of MeOH (2mL) and extracted with CH2Cl2 three times. The combined organic extracts were washed with brine and dried over MgSO4. After evaporating the solvent under reduced pressure, the product was purified by column chromatography on silica gel using petroleum ether/EtOAc (5:1; for 4η-nitroacetophenone: 5/3) as the eluent. The ee value was determined by HPLC with Chiralcel AS-3 or Chiralcel OD-H columns. With dimethylsulfide borane complex, 2-hydroxy-N-[(1S,2R)-2-hydroxy-1,2-diphenylethyl]benzamide in tetrahydrofuran, T= 65 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 95 percent; enantioselective reaction Turgut, Yilmaz; Azizoglu, Murat; Erdogan, Asli; Arslan, Nevin; Hosgoren, Halil; Tetrahedron Asymmetry; vol. 24; nb. 13-14; (2013); p. 853 - 859 View in Reaxys 4.3 General procedure for the enantioselective reduction of ketones with borane-dimethyl sulfide in the presence of ̈-hydroxyamides 1–7 General procedure: A 25mL two-necked flask was charged with η-hydroxyamide 1–7 (0.05mmol, 10percent) in dry and fresh THF (3mL), equipped with a magnetic stirrer and a connection to the combined nitrogen/vacuum line and closed with a septum. The air in the flask was replaced by nitrogen. η-hydroxyamides 1–7 were dissolved in THF (3mL) with stirring and a solution of BH3·SMe2 (0.5mmol, 10M) complex was added at 0°C by a syringe. After the mixture was stirred for 1h at 65°C, the freshly distilled ketone (0.5mmol) in freshly dried THF (2mL) was added over a period of 1.5h by a syringe at the same temperature. The reaction mixture was kept stirring at the 65°C until the ketone was completely consumed. After stirring for a further 30min at rt, the reaction mixture was quenched by the addition of MeOH (2mL) and extracted with CH2Cl2 three times. The combined organic extracts were washed with brine and dried over MgSO4. After evaporating the solvent under reduced pressure, the product was purified by column chromatography on silica gel using petroleum ether/EtOAc (5:1; for 4η-nitroacetophenone: 5/3) as the eluent. The ee value was determined by HPLC with Chiralcel AS-3 or Chiralcel OD-H columns.

159/258

2018-07-03 17:29:03

With dimethylsulfide borane complex, 2-hydroxy-N-[(1S)-2-hydroxy-1,2,2-triphenylethyl]benzamide in tetrahydrofuran, T= 65 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 95 percent; enantioselective reaction Turgut, Yilmaz; Azizoglu, Murat; Erdogan, Asli; Arslan, Nevin; Hosgoren, Halil; Tetrahedron Asymmetry; vol. 24; nb. 13-14; (2013); p. 853 - 859 View in Reaxys With 1,4-diaza-bicyclo[2.2.2]octane, [Ru(η6-p-cymene)(η2-o-{(11bS)-3H-dinaphtho(2,1-c:1',2'-e)phosphepin-4(5H)yl}C6H4SO3)Cl] in methanol, Time= 15h, T= 60 °C , p= 45004.5Torr , Autoclave, Mechanism, Overall yield = 98 percentChromat.; enantioselective reaction Jiang, Fan; Yuan, Kedong; Achard, Mathieu; Bruneau, Christian; Chemistry - A European Journal; vol. 19; nb. 31; (2013); p. 10343 - 10352 View in Reaxys With RuCl2(PPh3)2{(1S,1’S)-1,1’-biisoindoline}, potassium tert-butylate, hydrogen, triphenylphosphine in isopropyl alcohol, Time= 36h, T= 20 °C , p= 38002.6Torr , Autoclave, Noyori Asymmetric Hydrogenation, enantioselective reaction Zhou, Han; Huang, Hanmin; ChemCatChem; vol. 5; nb. 8; (2013); p. 2253 - 2257 View in Reaxys ATH of aromatic ketones General procedure: To a 50mL Schlenk tube were added Ir complex (0.005mmol) and ligand 5 (0.005mmol). Under nitrogen atmosphere, freshly distilled and degassed iPrOH (10mL) were introduced. After stirring at 40°C for 30min, an appropriate amount of KOH/iPrOH solution was then added. The mixture was continually stirred for another 15min, ketone was then introduced and the mixture was stirred at 40°C for a certain period of time. At the end of experiment, the reaction products were analyzed by GC using a chiral CP-Chiralsil-Dex CB column. With carbonylhydridotris(triphenylphosphine)iridium(I), C42H55N4O4P, isopropyl alcohol, potassium hydroxide, Time= 5h, T= 40 °C , Schlenk technique, Inert atmosphere, Reagent/catalyst, enantioselective reaction Xu, Ya-Qing; Yu, Shen-Luan; Li, Yan-Yun; Dong, Zhen-Rong; Gao, Jing-Xing; Chinese Chemical Letters; vol. 24; nb. 6; (2013); p. 527 - 530 View in Reaxys ATH of aromatic ketones General procedure: To a 50mL Schlenk tube were added Ir complex (0.005mmol) and ligand 5 (0.005mmol). Under nitrogen atmosphere, freshly distilled and degassed iPrOH (10mL) were introduced. After stirring at 40°C for 30min, an appropriate amount of KOH/iPrOH solution was then added. The mixture was continually stirred for another 15min, ketone was then introduced and the mixture was stirred at 40°C for a certain period of time. At the end of experiment, the reaction products were analyzed by GC using a chiral CP-Chiralsil-Dex CB column. With carbonylhydridotris(triphenylphosphine)iridium(I), C32H43N4P, isopropyl alcohol, potassium hydroxide, Time= 5h, T= 40 °C , Schlenk technique, Inert atmosphere, Reagent/catalyst, Time, enantioselective reaction Xu, Ya-Qing; Yu, Shen-Luan; Li, Yan-Yun; Dong, Zhen-Rong; Gao, Jing-Xing; Chinese Chemical Letters; vol. 24; nb. 6; (2013); p. 527 - 530 View in Reaxys With C40H41FeNP2, tris(3,5-dimethylphenyl)phosphine, potassium tert-butylate, hydrogen, copper diacetate in isopropyl alcohol, Time= 24h, T= 15 °C , p= 15001.5Torr , Inert atmosphere, Overall yield = 97 percent; Overall yield = 565 mg Krabbe, Scott W.; Hatcher, Mark A.; Bowman, Roy K.; Mitchell, Mark B.; McClure, Michael S.; Johnson, Jeffrey S.; Organic Letters; vol. 15; nb. 17; (2013); p. 4560 - 4563 View in Reaxys With formic acid, N-{(1R,2R)-2-[3-(3,5-dimethoxyphenyl)propylamino]-1,2-diphenylethyl}-4-methylbenzenesulfonamide ruthenium chloride, triethylamine, Time= 5h, T= 60 °C , Inert atmosphere, Time, Reagent/catalyst, Solvent Soni, Rina; Jolley, Katherine E.; Clarkson, Guy J.; Wills, Martin; Organic Letters; vol. 15; nb. 19; (2013); p. 5110 - 5113 View in Reaxys With dimethylsulfide borane complex, 2-hydroxy-N-[(2S)-1-hydroxy-1,1,3-triphenylpropan-2-yl]pyridine-3-carboxamide in tetrahydrofuran, T= 65 °C , Inert atmosphere, Catalytic behavior, Reagent/catalyst, Overall yield = 96 percent; enantioselective reaction

160/258

2018-07-03 17:29:03

Azizoglu, Murat; Erdogan, Asli; Arslan, Nevin; Turgut, Yilmaz; Chirality; vol. 26; nb. 1; (2014); p. 21 - 26 View in Reaxys With dimethylsulfide borane complex, 2-hydroxy-N-[(1R,2S)-2-hydroxy-2,3-dihydro-1H-inden-1-yl]pyridine-3-carboxamide in tetrahydrofuran, T= 65 °C , Inert atmosphere, Catalytic behavior, Reagent/catalyst, Overall yield = 96 percent; enantioselective reaction Azizoglu, Murat; Erdogan, Asli; Arslan, Nevin; Turgut, Yilmaz; Chirality; vol. 26; nb. 1; (2014); p. 21 - 26 View in Reaxys Stage 1: With lithium aluminium tetrahydride, C37H45BrFeNO2P2 (3+)*BF4 (1-), hydrogen in tetrahydrofuran, Time= 0.0833333h, T= 50 °C , p= 3800.26Torr Stage 2: in tetrahydrofuran, tert-Amyl alcohol, Time= 0.166667h Stage 3: With potassium tert-butylate in tetrahydrofuran, Inert atmosphere, Glovebox, Catalytic behavior, enantioselective reaction Lagaditis, Paraskevi O.; Sues, Peter E.; Sonnenberg, Jessica F.; Wan, Kai Yang; Lough, Alan J.; Morris, Robert H.; Journal of the American Chemical Society; vol. 136; nb. 4; (2014); p. 1367 - 1380 View in Reaxys Typical procedure for the asymmetric hydrogenation of ketones 7a–o11 General procedure: To a 20 mL hydrogenation vessel were added the catalyst precursor [{Ir(cod)Cl}2] (1.7 mg, 2.53 μmol), ligand 2f (4.5 mg, 6.06 μmol), and anhydrous EtOH (3 mL) under a nitrogen atmosphere. The mixture was stirred for 1.0 h at 25– 30 °C to give a clear yellow solution. After placing the vessel in an autoclave, the ketone (10 mmol) and t-BuOK (28 mg, 0.253 mmol) were added. The autoclave was replaced with H2 three times, and the reaction mixture was stirred at room temperature until no obvious hydrogen pressure drop was observed. After releasing the hydrogen pressure, the reaction mixture was filtered through a short silica gel column. The solvent in the filtrate was removed to determine the yield and the product obtained was analyzed by HPLC to determine the enantiomeric excess. With bis(1,5-cyclooctadiene)diiridium(I) dichloride, (RC,SFc)-1-[bis(3,5-di-tert-butylphenyl)phosphino]-2-[1-N-(6-methylpyridin-2-ylmethyl)aminoethyl] ferrocene, potassium tert-butylate, hydrogen in ethanol, Time= 15h, T= 25 - 30 °C , p= 15201Torr , Autoclave, Overall yield = 99 percent; enantioselective reaction Nie, Huifang; Zhou, Gang; Wang, Quanjun; Chen, Weiping; Zhang, Shengyong; Tetrahedron Asymmetry; vol. 24; nb. 24; (2013); p. 1567 - 1571 View in Reaxys With sodium t-butanolate, tert-butyl alcohol, (S)-2,2',6,6'-tetramethoxy-4,4'-bis(di(3,5-xylyl)phosphino)-3,3'-bipyridine in toluene, Time= 14h, T= 20 °C , Overall yield = 95 percent Li, Min; Li, Bin; Xia, Hong-Feng; Ye, Danru; Wu, Jing; Shi, Yifeng; Green Chemistry; vol. 16; nb. 5; (2014); p. 2680 - 2688 View in Reaxys 4.5 General procedure for the asymmetric reduction of ketones General procedure: In a Schlenk tube, the chiral ligand (0.05mmol) and the metallic precursor (0.025mmol) were dissolved in water (4mL). After one hour of stirring at 30°C, sodium formate (10mmol) and the ketone (1mmol) were added to the aqueous solution. The solution was maintained at 30°C until total reduction of the ketone. The formed alcohol was separated from the catalyst by simple extraction with pentane (2×8mL), and the organic layer was dried over MgSO4, and concentrated in vacuo. The crude residue was distilled in order to purify the alcohol. With dichloro(mesitylene)ruthenium(II) dimer, (1S,2R)-1-((E)-(3-(dimethyl(phenyl)silyl)-2-hydroxy-5-methoxybenzylidene)amino)-2,3-dihydro-1H-inden-2-ol, sodium formate in water, Time= 18h, T= 30 °C , Schlenk technique, Overall yield = 94 percent; enantioselective reaction Boukachabia, Mourad; Vriamont, Nicolas; Lambin, Dominique; Riant, Olivier; Aribi-Zouioueche, Louisa; Comptes Rendus Chimie; vol. 17; nb. 5; (2014); p. 403 - 412 View in Reaxys Asymmetric transfer hydrogenation in FA:TEA: To a mixture of catalyst (0.002 mmol) in FA:TEA (5:2) (1.0 mL) was added ketone (2.0 mmol) and the mixure was stirred at 60 °C for 24h under an inert atmosphere. The reaction was monitored by TLC. After 24h, the reaction mixture was diluted with EtOAc and sat. NaHC03 soln. The organic layer was separated, washed with H20, dried over anhy. Na2S04, filtered and concentrated to give a brown residue. The crude compound was analysed by 1H-NMR to give the conversion.

161/258

2018-07-03 17:29:03

With formic acid, N-{(1R,2R)-2-[3-(3,5-dimethoxyphenyl)propylamino]-1,2-diphenylethyl}-4-methylbenzenesulfonamide ruthenium chloride, triethylamine, Time= 1h, T= 60 °C , Inert atmosphere, Time Patent; THE UNIVERSITY OF WARWICK; WILLS, Martin; JOLLEY, Katherine Emma; SONI, Rina; WO2014/68331; (2014); (A1) English View in Reaxys 1.6 ATH of ketones catalyzed by chiral ruthenium(II) complex General procedure: A typical procedure for the ATH was as follows: Under a nitrogen atmosphere, the chiral ruthenium(II) complex (R,R)-3 (4.5 mg, 0.005 mmol) were placed in a Schlenk tube equipped with a Teflon-coated magnetic stirring bar. Isopropyl alcohol (iPrOH) was then added and the mixture was stirred at 65 °C for 30 min. An appropriate amount of KOH/iPrOH solution was then added, and the mixture was continually stirred for another 10 min. Ketone was then introduced and the mixture was stirred at the desired temperature for the required reaction time. At the end of the reaction, the product was determined by GC using a chiral CP-Chiralsil-Dex CB column. With ammonium iodide, C49H50Cl2N2P2Ru, potassium hydroxide in isopropyl alcohol, Time= 4h, T= 40 °C , Inert atmosphere, Schlenk technique, Reagent/catalyst, Temperature, Time, enantioselective reaction Zeng, Li; Wu, Fang; Li, Yan-Yun; Dong, Zhen-Rong; Gao, Jing-Xing; Journal of Organometallic Chemistry; vol. 762; (2014); p. 34 - 39 View in Reaxys 74 %Spectr. With C47H40O4P2Rh(1+)*CF3O3S(1-), diphenylsilane, hydrogen in tetrahydrofuran, Time= 1h, T= 20 °C , p= 15001.5Torr , Inert atmosphere, Autoclave, Pressure, Solvent, enantioselective reaction Balan, Cedric; Pop, Roxana; Comte, Virginie; Poinsot, Didier; Ratovelomanana-Vidal, Virginie; Gendre, Pierre Le; Applied Organometallic Chemistry; vol. 28; nb. 7; (2014); p. 517 - 522 View in Reaxys 60 %Spectr. With C47H40O4P2Rh(1+)*CF3O3S(1-), diphenylsilane, hydrogen in dichloromethane, Time= 1h, T= 20 °C , p= 15001.5Torr , Inert atmosphere, Autoclave, enantioselective reaction Balan, Cedric; Pop, Roxana; Comte, Virginie; Poinsot, Didier; Ratovelomanana-Vidal, Virginie; Gendre, Pierre Le; Applied Organometallic Chemistry; vol. 28; nb. 7; (2014); p. 517 - 522 View in Reaxys With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, (S,S,S,S)-N,N-bis(1,2-diphenylethylenediamino)-1,3-benzenedisulfonylamine, sodium formate in water, Time= 11h, T= 60 °C , Inert atmosphere, Reagent/catalyst, enantioselective reaction Liu, Xungao; Zhang, Tian; Hu, Yingying; Shen, Liang; Catalysis Letters; vol. 144; nb. 7; (2014); p. 1289 - 1295 View in Reaxys Heterogeneous enantioselective hydrogenation reaction; general procedure General procedure: The hydrogenation was performed in a 20 mL stainless autoclave with a magnetic stirrer bar. The desired amounts of 1.0percentRu/η-Al2O3/2tpp(20 mg), iPrOH (2 mL), KOH (0.18 mol L–1), L-proline derivative 1 and substrate (Substrate/Ru/proline derivative 1 = 300 : 1 : 27.4) were added into the autoclave and this was then sealed and purged with pure hydrogen several times (reaction pressure, PH2: 6.0 MPa). After the reactants were heated to 30 °C, the reaction timing began. After completion of the reaction (10 h), the organic phase was dried over MgSO4 and the conversion and enantiomeric excess were determined by GC analysis according to literature.17 With the exception of aromatic alcohol, no other products were detected (GC–MS and NMR). With Ru/Al2O3/2ttp, hydrogen, potassium hydroxide, (2S)-N-phenylpyrrolidine-2-carboxamide in isopropyl alcohol, Time= 10h, T= 30 °C , p= 45004.5Torr , Autoclave, Overall yield = 51 percent; enantioselective reaction Jiang, Heyan; Journal of Chemical Research; vol. 38; nb. 7; (2014); p. 410 - 413 View in Reaxys With bis(1,5-cyclooctadiene)diiridium(I) dichloride, hydrogen, triphenylphosphine, lithium hydroxide, 9-amino-9-deoxyepicinchonine in ethanol, Time= 2h, T= 25 °C , p= 45004.5Torr , Autoclave, enantioselective reaction Li, Chun; Zhang, Lin; Du, You; Zheng, Xue-Li; Fu, Hai-Yan; Chen, Hua; Li, Rui-Xiang; Catalysis Communications; vol. 28; (2012); p. 5 - 8 View in Reaxys

162/258

2018-07-03 17:29:03

With C44H52FeN4P2 (2+)*2BF4 (1-), sodium t-butanolate in isopropyl alcohol, Time= 15h, T= 75 °C , Glovebox, Schlenk technique, Inert atmosphere, Overall yield = 95 percent; Overall yield = 74 percentChromat.; enantioselective reaction Bigler, Raphael; Mezzetti, Antonio; Organic Letters; vol. 16; nb. 24; (2014); p. 6460 - 6463 View in Reaxys Screening procedure General procedure: Erlenmeyer flasks (300 ml), each containing 100 ml of the medium consisting of 3 g glucose and 1 g aminobac dissolved in water,were inoculated with a suspension of microorganisms and then incubated for 3–7 days at 25 C on a rotary shaker (190 rpm). After full growth of the culture 20 mg of a substrate dissolved in 1 ml of acetone was added. After 1, 3, 6, 9, 12 h and 1, 3, 6, 9 days of incubation under the above conditions, portions of 5 ml of the transformation mixture were taken out and extracted with CHCl3(3*10 ml). The extracts were dried over MgSO4, concentrated in vacuo, and analyzed by GC. All the experiments were repeatedthree times. With yeast culture of Rhodotorula rubra KCh 4 in acetone, Time= 216h, T= 25 °C , Microbiological reaction, Reagent/catalyst, Overall yield = 98 percentChromat.; enantioselective reaction Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Screening procedure General procedure: Erlenmeyer flasks (300 ml), each containing 100 ml of the medium consisting of 3 g glucose and 1 g aminobac dissolved in water,were inoculated with a suspension of microorganisms and then incubated for 3–7 days at 25 C on a rotary shaker (190 rpm). After full growth of the culture 20 mg of a substrate dissolved in 1 ml of acetone was added. After 1, 3, 6, 9, 12 h and 1, 3, 6, 9 days of incubation under the above conditions, portions of 5 ml of the transformation mixture were taken out and extracted with CHCl3(3*10 ml). The extracts were dried over MgSO4, concentrated in vacuo, and analyzed by GC. All the experiments were repeatedthree times. With yeast culture of Yarrowia lipolytica 1-101-1,31-K1 in acetone, Time= 216h, T= 25 °C , Microbiological reaction, Reagent/ catalyst, Overall yield = 94 percentChromat.; enantioselective reaction Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 2 1: sodium tetrahydroborate / methanol 2: yeast culture of Yarrowia lipolytica KCh 71 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Typical procedure for the reduction of prochiral ketones General procedure: ketonesBH3/SMe2(1.1 ml, 1 M) was added by syringe to a solution ofchiral polyether ligand Poly-6 (0.78 g, 0.1 mmol) in dry THF (5 ml)under nitrogen at 0C. The mixture was stirred for 1 h at 0C andthen a solution of ketone (1 mmol) in dry THF (5 ml) was addeddropwise over a period of 1 h at the same temperature and stirredfor 6 h, the reaction mixture was then quenched by dropwise addi-tion of 10percent NH4Cl (5 ml). The alcohol product was isolated byextraction with ethyl acetate (10 ml × 3). The organic phase waswashed with brine, dried over anhydrous sodium sulfate. Afterconcentration by rotatory evaporation, the product was purifiedby column chromatography on silica gel (petroleum ether/ethylacetate 6:1) to afford the corresponding alcohol. The enantiomericexcesses were determined by HPLC with a chiral column (Dai-cel Chiralcel OD-H; eluent, hexane-isopropyl alcohol; UV detector,254 nm). With tetrahydrofuran, dimethylsulfide borane complex in toluene, T= 0 °C , Inert atmosphere, Overall yield = 90 percent; enantioselective reaction Zhang, An-Lin; Yu, Zeng-Da; Yang, Li-Wen; Yang, Nian-Fa; Peng, Dan; Journal of Molecular Catalysis A: Chemical; vol. 398; (2015); p. 407 - 412 View in Reaxys With trimethylamine-N-oxide, C38H38FeO6Si2, hydrogen in water, isopropyl alcohol, Time= 18h, T= 70 °C , p= 22502.3Torr , Inert atmosphere, Autoclave, Schlenk technique, enantioselective reaction

163/258

2018-07-03 17:29:03

Gajewski, Piotr; Renom-Carrasco, Marc; Facchini, Sofia Vailati; Pignataro, Luca; Lefort, Laurent; De Vries, Johannes G.; Ferraccioli, Raffaella; Forni, Alessandra; Piarulli, Umberto; Gennari, Cesare; European Journal of Organic Chemistry; vol. 2015; nb. 9; (2015); p. 1887 - 1893 View in Reaxys 2.2. General procedure of asymmetric reduction of ketones General procedure: In a schlenk tube, BH3·SMe2(0.55 mmol, 275 L) was added inthe solution of IL 5 (28 mg, 10 molpercent) dissolved in THF (1 mL), undernitrogen atmosphere. The homogenous mixture was stirred andheated at 70C for 30 min. Later, a solution of ketone (0.5 mmolin THF (0.5 mL)) was added within 30 min. After the addition wascompleted, the solvent was evaporated under vacuum. An aqueoussolution of 1M HCl (5 mL) was added and the product was extractedwith DCM. The solvent was dried on anhydrous sodium sulfateand evaporated under reduced pressure. Crude residue was furtherpurified by column chromatography on silica gel using hexane-ethyl acetate as eluent. Enantiomeric excesses of all alcohols weredetermined by HPLC analysis using Chiralcel OD–H/AD–H chiralcolumn, isopropanol-n-hexane as mobile phase and HPLC condi-tions are given in SI. Stage 1: With dimethylsulfide borane complex, 3-(5-((3R,5S)-5-(hydroxydiphenylmethyl)pyrrolidin-3-yloxy)-5-oxopentyl)-1methyl-1H-imidazol-3-ium hexafluorophosphate in tetrahydrofuran, Time= 0.5h, T= 70 °C , Inert atmosphere, Schlenk technique Stage 2: With hydrogenchloride in water, Inert atmosphere, Schlenk technique, Overall yield = 92 percent Chauhan, ManMohan Singh; Singh, Surendra; Journal of Molecular Catalysis A: Chemical; vol. 398; (2015); p. 184 - 189 View in Reaxys Stage 1: With [dibenzhydryl-(S)-tBu-(iminopyridine-oxazoline)]FeBr2, diphenylsilane, sodium triethylborohydride in toluene, Time= 3h, T= 25 °C , Inert atmosphere, Schlenk technique Stage 2: With sodium hydroxide in methanol, water, toluene, Time= 10h, Overall yield = 79 percent; Overall yield = 54 mg; enantioselective reaction Zuo, Ziqing; Zhang, Lei; Leng, Xuebing; Huang, Zheng; Chemical Communications; vol. 51; nb. 24; (2015); p. 5073 - 5076 View in Reaxys With C33H47IrN3 (1+)*F6P(1-), sodium t-butanolate in isopropyl alcohol, Time= 8h, T= 30 °C , Schlenk technique, Inert atmosphere, Reagent/catalyst, Overall yield = 56 percentChromat.; Optical yield = 24 percent ee; enantioselective reaction Sabater, Sara; Baya, Miguel; Mata, Jose A.; Organometallics; vol. 33; nb. 23; (2014); p. 6830 - 6839 View in Reaxys With (R)-N-(3-amino-3-phenylpropyl)-4-methylbenzenesulfonamide, C10H14*Ru(1+)*Cl(1-)*C16H20N2O2S, sodium formate in water, dimethyl sulfoxide, Time= 48h, T= 40 °C , Schlenk technique, enantioselective reaction Facchetti, Giorgio; Gandolfi, Raffaella; Fusè, Marco; Zerla, Daniele; Cesarotti, Edoardo; Pellizzoni, Michela; Rimoldi, Isabella; New Journal of Chemistry; vol. 39; nb. 5; (2015); p. 3792 - 3800 View in Reaxys With (S)-N-(3-amino-1-phenylpropyl)-4-methylbenzenesulfonamide, C10H14*Ru(1+)*Cl(1-)*C16H20N2O2S, sodium formate in water, dimethyl sulfoxide, Time= 48h, T= 40 °C , Schlenk technique, enantioselective reaction Facchetti, Giorgio; Gandolfi, Raffaella; Fusè, Marco; Zerla, Daniele; Cesarotti, Edoardo; Pellizzoni, Michela; Rimoldi, Isabella; New Journal of Chemistry; vol. 39; nb. 5; (2015); p. 3792 - 3800 View in Reaxys With trimethylamine-N-oxide, C38H38FeO6Si2, hydrogen in water, isopropyl alcohol, Time= 18h, T= 70 °C , p= 22502.3Torr , Autoclave, enantioselective reaction Gajewski, Piotr; Renom-Carrasco, Marc; Facchini, Sofia Vailati; Pignataro, Luca; Lefort, Laurent; De Vries, Johannes G.; Ferraccioli, Raffaella; Piarulli, Umberto; Gennari, Cesare; European Journal of Organic Chemistry; vol. 2015; nb. 25; (2015); p. 5526 - 5536 View in Reaxys With glyceline, alcohol dehydrogenase from ralstonia sp, NADP, isopropyl alcohol in aq. phosphate buffer, Time= 24h, T= 30 °C , pH= 7.5, Green chemistry, Enzymatic reaction, Reagent/catalyst, enantioselective reaction Müller, Christoph R.; Lavandera, Iván; Gotor-Fernández, Vicente; Domínguezdemaría, Pablo; ChemCatChem; vol. 7; nb. 17; (2015); p. 2654 - 2659

164/258

2018-07-03 17:29:03

View in Reaxys 2.4 Asymmetric bioreduction process General procedure: The standard reaction mixture contained 10mM substrate, Na2HPO4–NaH2PO4 buffer (100 mM, pH 7.0), 2.5 mM NADH and an appropriate amount of E. brevis ZJUY-1401 cells in a total volume of 1.0 ml. The biotransformations were carried out at 30°C with shaking at 200 rpm. Samples were centrifuged and the supernatants were extracted with ethyl acetate. The organic layer was dried over anhydrous Na2SO4. The conversion and enantiomeric excess of product (eep) were determined by chiral gas chromatography (GC) or high-performance liquid chromatography (HPLC) analyses. All experiments were conducted in triplicate if not specified. With ethanol, NADH in aq. buffer, Time= 15h, T= 35 °C , pH= 7, Microbiological reaction, Enzymatic reaction, stereoselective reaction Li, Aipeng; Ye, Lidan; Guo, Fei; Yang, Xiaohong; Yu, Hongwei; Journal of Molecular Catalysis B: Enzymatic; vol. 117; (2015); p. 31 - 37 View in Reaxys With sodium isopropylate, isopropyl alcohol, Time= 1h, T= 20 °C , Reflux, Overall yield = 97 percentChromat.; Optical yield = 82 percent ee Kucukturkmen, Cigdem; Agac, Ahmet; Eren, Aysel; Karakaya, Idris; Aslantas, Mehmet; Celik, Omer; Ulukanli, Sabri; Karabuga, Semistan; Catalysis Communications; vol. 74; (2016); p. 122 - 125 View in Reaxys Stage 1: With silver tetrafluoroborate, diethoxymethylane, C30H39ClIrN3O2 in tetrahydrofuran, Time= 15h, T= 20 °C Stage 2: With potassium carbonate in tetrahydrofuran, methanol, Time= 2h, T= 20 °C , Reagent/catalyst, Overall yield = 92 percent; enantioselective reaction Shinohara, Kanako; Kawabata, Shun; Nakamura, Hanako; Manabe, Yoshiki; Sakaguchi, Satoshi; European Journal of Organic Chemistry; vol. 2014; nb. 25; (2014); p. 5532 - 5539 View in Reaxys Stage 1: With silver tetrafluoroborate, diethoxymethylane, chloro(η4-1,5-cyclooctadiene)[3-(2-{[(1S)-2-methoxy-1-methylethyl]amino}-2-oxoethyl)-1-phenylmethylbenzimidazole-2-ylidene]iridium(I) in tetrahydrofuran, Time= 15h, T= 20 °C Stage 2: With potassium carbonate in tetrahydrofuran, methanol, Time= 2h, T= 20 °C , Reagent/catalyst, Overall yield = 32 percent; enantioselective reaction Shinohara, Kanako; Kawabata, Shun; Nakamura, Hanako; Manabe, Yoshiki; Sakaguchi, Satoshi; European Journal of Organic Chemistry; vol. 2014; nb. 25; (2014); p. 5532 - 5539 View in Reaxys 2.3.1. Procedure using [IrCl(cod)]2as an Ir catalyst precursor General procedure: A flask was charged with azolium salt L12 (0.02 mmol, 9.1 mg),Ag2O (0.01 mmol, 2.4 mg) and CH2Cl2(1 mL). After stirring the resulting mixture at room temperature for 2 h in the dark, CH2Cl2 was removed in vacuo. Then, a THF (1 mL) solution of [IrCl(cod)]2(0.01 mmol, 6.9 mg) was added to the reaction vessel. The resulting mixture was stirred at room temperature for an additional 4 h in the dark, filtered through a membrane filter, and evaporated to dry-ness in vacuo. Subsequently, to the resulting flask containing yellow solid of the unpurified IrCl(cod)(NHC) complex, a solution of AgBF4(0.025 mmol, 4.9 mg) in CPME (2 mL) was added, and then stirred at room temperature for 1 h. Finally, propiophenone (0.5 mmol,66 mg) and (EtO)2MeSiH (2.25 mmol, 294 mg) were added to the resulting CPME solution (see Appendix A. Supplementary data fordetails). After stirring at room temperature for 20 h under open-air conditions, K2CO3(2 mg) and MeOH (2 mL) were added. Then, the resulting mixture was stirred at room temperature for 2 h. Afterevaporation of the solvents, the residue obtained was purified bycolumn chromatography on silica gel (Et2O/n-hexane = 3:7) to give(S)-1-phenyl-1-propanol (61 mg, 91percent isolated yield). The ee was measured by chiral GLC. With silver tetrafluoroborate, diethoxymethylane, C19H29N3O2*Cl(1-)*Ir(1+)*C8H12, Time= 20h, T= 20 °C , Overall yield = 13 percentChromat.; stereoselective reaction Manabe, Yoshiki; Shinohara, Kanako; Nakamura, Hanako; Teramoto, Hiro; Sakaguchi, Satoshi; Journal of Molecular Catalysis A: Chemical; vol. 421; (2016); p. 138 - 145 View in Reaxys 2.3.1. Procedure using [IrCl(cod)]2as an Ir catalyst precursor General procedure: A flask was charged with azolium salt L12 (0.02 mmol, 9.1 mg),Ag2O (0.01 mmol, 2.4 mg) and CH2Cl2(1 mL). After stirring the resulting mixture at room temperature for 2 h in the dark, CH2Cl2 was removed in vacuo. Then, a THF (1

165/258

2018-07-03 17:29:03

mL) solution of [IrCl(cod)]2(0.01 mmol, 6.9 mg) was added to the reaction vessel. The resulting mixture was stirred at room temperature for an additional 4 h in the dark, filtered through a membrane filter, and evaporated to dry-ness in vacuo. Subsequently, to the resulting flask containing yellow solid of the unpurified IrCl(cod)(NHC) complex, a solution of AgBF4(0.025 mmol, 4.9 mg) in CPME (2 mL) was added, and then stirred at room temperature for 1 h. Finally, propiophenone (0.5 mmol,66 mg) and (EtO)2MeSiH (2.25 mmol, 294 mg) were added to the resulting CPME solution (see Appendix A. Supplementary data fordetails). After stirring at room temperature for 20 h under open-air conditions, K2CO3(2 mg) and MeOH (2 mL) were added. Then, the resulting mixture was stirred at room temperature for 2 h. Afterevaporation of the solvents, the residue obtained was purified bycolumn chromatography on silica gel (Et2O/n-hexane = 3:7) to give(S)-1-phenyl-1-propanol (61 mg, 91percent isolated yield). The ee was measured by chiral GLC. With silver tetrafluoroborate, diethoxymethylane, C23H29N3O2*Cl(1-)*Ir(1+)*C8H12, Time= 20h, T= 20 °C , Reagent/catalyst, Overall yield = 77 percentChromat.; stereoselective reaction Manabe, Yoshiki; Shinohara, Kanako; Nakamura, Hanako; Teramoto, Hiro; Sakaguchi, Satoshi; Journal of Molecular Catalysis A: Chemical; vol. 421; (2016); p. 138 - 145 View in Reaxys With 2-[(6-methylpyridin-2-yl-methyl)amino]-3-phenylprop-1-oxyiridium(I) cyclooctadiene, potassium tert-butylate, hydrogen, acetone in tetrahydrofuran, Time= 48h, T= 20 °C , p= 15001.5Torr , Autoclave, Optical yield = 64 percent ee; enantioselective reaction Kumar, Prashant; Irrgang, Torsten; Kostakis, George E.; Kempe, Rhett; RSC Advances; vol. 6; nb. 45; (2016); p. 39335 39342 View in Reaxys General method for the enantioselective reduction of aromatic ketones with borane-dimethyl sulfide in the presence of ̈hydroxyamides 1–7 General procedure: A 25mL two-necked flask was charged with η-hydroxyamide 1–7 (0.05mmol, 10percent) in dry and freshly distilled THF (3mL), equipped with a magnetic stirrer and a connection to a combined nitrogen/vacuum line and closed with a septum. The air in the flask was replaced by nitrogen. η-Hydroxyamides 1–7 were dissolved in THF (3mL) under stirring after which a solution of BH3.SMe2 (0.5mmol, 10M) complex was added at 0°C by a syringe. After the mixture was stirred for 1h at 65°C, the freshly distilled ketone (0.5mmol) in dry and freshly distilled THF (2mL) was added over a period of 1.5h by syringe at the same temperature. The reaction mixture was stirred at 65°C until the ketone was completely consumed. After stirring for a further 30min at rt, the reaction mixture was quenched by the addition of MeOH (2mL) and extracted with CH2Cl2 (3×3mL). The combined organic extracts were washed with brine and dried over MgSO4. After evaporating the solvent under reduced pressure, the product was purified by column chromatography on silica gel using petroleum ether/EtOAc (5:1; for 4η-nitroacetophenone: 5/3) as eluent. The ee value was determined by HPLC with Chiralcel AS-3 or Chiralcel OD-H columns With dimethylsulfide borane complex, 3-hydroxy-N-[(1R,2S)-cis-2-hydroxy-2,3-dihydro-1H-inden-1-yl]naphthalene-2-carboxamide in tetrahydrofuran, T= 65 °C , Inert atmosphere, Catalytic behavior, Reagent/catalyst, Overall yield = 96 percent; enantioselective reaction Azizoglu, Murat; Erdogan, Aslı; Arslan, Nevin; Turgut, Yılmaz; Hosgoren, Halil; Pirinccioglu, Necmettin; Tetrahedron Asymmetry; vol. 27; nb. 14-15; (2016); p. 614 - 622 View in Reaxys General method for the enantioselective reduction of aromatic ketones with borane-dimethyl sulfide in the presence of ̈hydroxyamides 1–7 General procedure: A 25mL two-necked flask was charged with η-hydroxyamide 1–7 (0.05mmol, 10percent) in dry and freshly distilled THF (3mL), equipped with a magnetic stirrer and a connection to a combined nitrogen/vacuum line and closed with a septum. The air in the flask was replaced by nitrogen. η-Hydroxyamides 1–7 were dissolved in THF (3mL) under stirring after which a solution of BH3.SMe2 (0.5mmol, 10M) complex was added at 0°C by a syringe. After the mixture was stirred for 1h at 65°C, the freshly distilled ketone (0.5mmol) in dry and freshly distilled THF (2mL) was added over a period of 1.5h by syringe at the same temperature. The reaction mixture was stirred at 65°C until the ketone was completely consumed. After stirring for a further 30min at rt, the reaction mixture was quenched by the addition of MeOH (2mL) and extracted with CH2Cl2 (3×3mL). The combined organic extracts were washed with brine and dried over MgSO4. After evaporating the solvent under reduced pressure, the product was purified by column chromatography on silica gel using petroleum ether/EtOAc (5:1; for 4η-nitroacetophenone: 5/3) as eluent. The ee value was determined by HPLC with Chiralcel AS-3 or Chiralcel OD-H columns With dimethylsulfide borane complex, 3-hydroxy-N-[(1S)-2-hydroxy-1,2,2-triphenylethyl]naphthalene-2-carboxamide in tetrahydrofuran, T= 65 °C , Inert atmosphere, Catalytic behavior, Reagent/catalyst, Overall yield = 96 percent; enantioselective reaction

166/258

2018-07-03 17:29:03

Azizoglu, Murat; Erdogan, Aslı; Arslan, Nevin; Turgut, Yılmaz; Hosgoren, Halil; Pirinccioglu, Necmettin; Tetrahedron Asymmetry; vol. 27; nb. 14-15; (2016); p. 614 - 622 View in Reaxys Typical preparative scalereactions using TbSADH best mutant General procedure: A test tube (10 mL)containing LB (4 mL) and kanamycin (50 µg/mL) was inoculated with mutant SZ2074 and incubated 8h (37°C, 220 rpm). The pre-culture was then inoculated intoTB (400 mL) containing kanamycin (50 µg/mL) and allowed to grow at 37°C until O.D.was ca. 0.6. IPTG was then added to a final concentration of 0.2 mM and theculture was grown for 16 h (30°C, 180 rpm). Cells were pelleted bycentrifugation, washed once with pH=7.4 potassium phosphate buffer (100 mM) andthen resuspended in pH=7.4 potassium phosphate buffer (45 mL, 100 mM). Cellswere then transferred to a 50 mL Erlenmeyer flask and 1.4 mg/mL lysozyme (70mg), 6U DNase I (50 µL), NADP+ 100mM (200 µL) were added. Substrate 3a (30 mM) in 10percent isopropanol (5 mL)was then added. Biotransformation was carried out at 30°C, 220rpm. GC controlindicated a 92percent conversion after 4h. The reaction was stopped after 6h when theconversion was 94percent. The organic phase was extracted with ethyl acetate (3x100mL) and crude reaction product was purified using column chromatography. (EA:PE1:4, Rf=0.55) afforded (R)-4a as a colourless liquid (157 mg,yield=75percent). With alcohol dehydrogenase TbSADH from Thermoanaerobacter brockii I86L/L294N mutant in aq. phosphate buffer, isopropyl alcohol, T= 30 °C , Enzymatic reaction, Reagent/catalyst, enantioselective reaction Sun, Zhoutong; Li, Guangyue; Ilie, Adriana; Reetz, Manfred T.; Tetrahedron Letters; vol. 57; nb. 32; (2016); p. 3648 - 3651 View in Reaxys Typical preparative scalereactions using TbSADH best mutant General procedure: A test tube (10 mL)containing LB (4 mL) and kanamycin (50 µg/mL) was inoculated with mutant SZ2074 and incubated 8h (37°C, 220 rpm). The pre-culture was then inoculated intoTB (400 mL) containing kanamycin (50 µg/mL) and allowed to grow at 37°C until O.D.was ca. 0.6. IPTG was then added to a final concentration of 0.2 mM and theculture was grown for 16 h (30°C, 180 rpm). Cells were pelleted bycentrifugation, washed once with pH=7.4 potassium phosphate buffer (100 mM) andthen resuspended in pH=7.4 potassium phosphate buffer (45 mL, 100 mM). Cellswere then transferred to a 50 mL Erlenmeyer flask and 1.4 mg/mL lysozyme (70mg), 6U DNase I (50 µL), NADP+ 100mM (200 µL) were added. Substrate 3a (30 mM) in 10percent isopropanol (5 mL)was then added. Biotransformation was carried out at 30°C, 220rpm. GC controlindicated a 92percent conversion after 4h. The reaction was stopped after 6h when theconversion was 94percent. The organic phase was extracted with ethyl acetate (3x100mL) and crude reaction product was purified using column chromatography. (EA:PE1:4, Rf=0.55) afforded (R)-4a as a colourless liquid (157 mg,yield=75percent). With alcohol dehydrogenase TbSADH from Thermoanaerobacter brockii I86N/C295N mutant in aq. phosphate buffer, isopropyl alcohol, T= 30 °C , Enzymatic reaction, Reagent/catalyst, enantioselective reaction Sun, Zhoutong; Li, Guangyue; Ilie, Adriana; Reetz, Manfred T.; Tetrahedron Letters; vol. 57; nb. 32; (2016); p. 3648 - 3651 View in Reaxys 2.4 General procedure for the catalytic transferhydrogenation reaction General procedure: To a solution of a ruthenium catalyst (0.0168 mmol)in degassed water (8 mL) was added a ketone (0.168mmol) and sodium formate (0.84 mmol). The reactionmixture was kept in a thermostat at 60°C. 1 mL of thesolution from the reaction mixture was withdrawn at 1 h,2 h and 12 h; extracted with 5 mL of ethyl acetate;dried over anhydrous sodium sulphate and analyzedby 1H NMR spectroscopy. Conversion was calculatedfrom the 1H NMR spectrum. Chiral alcohols were purifiedby preparative thin layer chromatography. Enantiomericexcess (ee) was determined using the chiralHPLC technique employing the Chiralcel OD column,except in the case of 1-(4-Chlorophenyl)ethanol, 1-(2-Chlorophenyl)ethanol, 1-(4-Nitrophenyl)ethanol), forwhich it was determined using a Chiralcel OJ-Hcolumn. With C21H30ClN2Ru(1+)*Cl(1-), sodium formate in water, Time= 12h, T= 60 °C , Inert atmosphere, Schlenk technique, Reagent/ catalyst, Time, Overall yield = 81 percent; enantioselective reaction Pandia Kumar, Arun Kumar; Samuelson, Ashoka G; Journal of Chemical Sciences; vol. 128; nb. 9; (2016); p. 1405 - 1415 View in Reaxys With ketoreductase P2-C11, NADPH in aq. phosphate buffer, isopropyl alcohol, Time= 24h, T= 30 °C , pH= 7, Enzymatic reaction, Reagent/catalyst, enantioselective reaction Ríos-Lombardía, Nicolás; Vidal, Cristian; Liardo, Elisa; Morís, Francisco; García-Álvarez, Joaquín; González-Sabín, Javier; Angewandte Chemie - International Edition; vol. 55; nb. 30; (2016); p. 8691 - 8695; Angew. Chem.; vol. 128; nb. 30; (2016); p. 8833 - 8837,5 View in Reaxys

167/258

2018-07-03 17:29:03

With ketoreductase P2-D11, NADPH in aq. phosphate buffer, isopropyl alcohol, Time= 24h, T= 30 °C , pH= 7, Enzymatic reaction, Reagent/catalyst, enantioselective reaction Ríos-Lombardía, Nicolás; Vidal, Cristian; Liardo, Elisa; Morís, Francisco; García-Álvarez, Joaquín; González-Sabín, Javier; Angewandte Chemie - International Edition; vol. 55; nb. 30; (2016); p. 8691 - 8695; Angew. Chem.; vol. 128; nb. 30; (2016); p. 8833 - 8837,5 View in Reaxys With (S,S)-trans-[FeCl(CO)-(PPh2CH2CH2NHCHPhCHPhNCHCH2PPh2)]BPh4, tetrabutylammonium tetrafluoroborate, water, potassium formate in 2-methyltetrahydrofuran, Time= 1h, T= 65 °C , Inert atmosphere, Schlenk technique, Overall yield = 93 percent; enantioselective reaction Demmans; Ko; Morris; RSC Advances; vol. 6; nb. 91; (2016); p. 88580 - 88587 View in Reaxys 4.3. General procedure for the asymmetric hydrogenation ofketones General procedure: To a solution of the substrate (1 mmol) dissolved under argon in degassed isopropanol (2.5 mL) was added the appropriate catalyst (5percent) dissolved in degassed isopropanol (2.5 mL). KtOBu (4percent) was added and the reaction mixture was transferred through a stainless steel capillary into a steel autoclave. The argon gas was then replaced by hydrogen gas (3-5 cycles) and the pressure was set. All hydrogenations were carried out for 18 h at r.t. under hydrogen gas at a pressure of 20 bar. After completion of the reaction, diethyl ether (10 mL) was added and the reaction was quenched by the addition of an aqueous solution of H3PO4 (20percent). The organic phase was separated, washed with brine, dried over MgSO4 and filtered through a plug of aluminium oxide. Conversions and e.e. values for the product were determined by GC on Supelco, Beta DexTM 110 (30 m) column (Table 1). With C51H45Fe3N3OP2 (2+)*2BF4 (1-), potassium tert-butylate, hydrogen in isopropyl alcohol, Time= 18h, T= 20 °C , p= 15001.5Torr , Inert atmosphere, Schlenk technique, Autoclave, Reagent/catalyst, Optical yield = 27 percent ee Zirakzadeh, Afrooz; de Aguiar, Sara R.M.M.; Widhalm, Michael; Mereiter, Kurt; Kirchner, Karl; Journal of Organometallic Chemistry; vol. 819; (2016); p. 260 - 265 View in Reaxys 4.1.4. General procedure for the asymmetric transfer hydrogenationreaction General procedure: Ruthenium complex (3.7 mg, 0.004 mmol), ketone (2 mmol) andNaOiPr (0.4 mL, 0.1 M) were dissolved in degassed iPrOH (10 mL) and the mixture was stirred under nitrogen atmosphere at appropriate temperature. A small volume of sample was taken from reaction mixture and diluted with diethyl ether (1:1), and rapidly filtered using a short silica pad. The conversion and enantiomeric excess were determined by GC using Agilent HP-Chiral 20B column(30 m, 0.25 mm, 0.25 mm) and by HPLC using Supelco AD-H, OD-Hchiral columns. With C50H47Cl2N3P2Ru, C50H47Cl2N3P2Ru, sodium isopropylate, isopropyl alcohol, Time= 0.2h, T= 20 °C , Inert atmosphere, enantioselective reaction Agac, Ahmet; Karakaya, Idris; Sahin, Irfan; Emir, Sedat; Karabuga, Semistan; Ulukanli, Sabri; Journal of Organometallic Chemistry; vol. 819; (2016); p. 189 - 193 View in Reaxys With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)], C70H73N4P3, potassium hydroxide in isopropyl alcohol, Time= 0.5h, T= 40 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 95 percentChromat.; enantioselective reaction Tao, Meng; Wu, Fang; Li, Teng; Li, Yan-Yun; Gao, Jing-Xing; Chinese Chemical Letters; vol. 28; nb. 1; (2017); p. 97 - 100 View in Reaxys With C39H44BrFe2NOP2, potassium tert-butylate, hydrogen in isopropyl alcohol, Time= 16h, p= 15001.5Torr , Autoclave, Reagent/catalyst, enantioselective reaction Zirakzadeh, Afrooz; Kirchner, Karl; Roller, Alexander; Stöger, Berthold; Widhalm, Michael; Morris, Robert H.; Organometallics; vol. 35; nb. 21; (2016); p. 3781 - 3787 View in Reaxys 4.10. Transfer hydrogenation of acetophenone. General procedure General procedure: In a two-neck flask (25 mL), under an inert atmosphere, wereplaced a catalyst solution (0.05 M in isopropanol, 100 lL, 5 lmol),a degassed 0.125 M solution of sodium hydroxide or potassium tert-butoxide in isopropanol (1 mL, 0.125 mmol), and degassed isopropanol(4 mL). After stirring for 15 min. at room temperature acetophenone (120 mg, 1 mmol) was

168/258

2018-07-03 17:29:03

added and the reaction mixture was refluxed for 30 min. Isopropanol was removed on rotary evaporator and 1-phenylethanol was isolated by flash column chromatography on silica gel (eluent: n-hexane:ethyl acetate80:20). With tris(triphenylphosphine)ruthenium(II) chloride, (3aS,5R,7R,7aR)-2-(2-(diphenylphosphino)phenyl)-6,6,7a-trimethyl-3a,4,5,6,7,7a-hexahydro-5,7-methanobenzo[d]oxazole, isopropyl alcohol, sodium hydroxide, Time= 0.5h, Inert atmosphere, Reflux, Overall yield = 93 percent; enantioselective reaction Kmieciak, Anna; Krzemiński, Marek P.; Tetrahedron Asymmetry; vol. 28; nb. 3; (2017); p. 467 - 472 View in Reaxys With 1,4-di-tert-butylbenzene, [Ru1,2,3,4,5-pentamethylcyclopentadienyl(((S,S)-MeNC3H2NCHPhCHPhNH2))(MeCN)](PF6), potassium tert-butylate, hydrogen in isopropyl alcohol, Time= 0.5h, T= 50 °C , p= 18751.9Torr , Glovebox, Catalytic behavior Wan, Kai Y.; Sung, Molly M. H.; Lough, Alan J.; Morris, Robert H.; ACS Catalysis; vol. 7; nb. 10; (2017); p. 6827 - 6842 View in Reaxys With C40H43BrFeMnNO2P2, potassium tert-butylate in isopropyl alcohol, Time= 6h, T= 25 °C , enantioselective reaction Zirakzadeh, Afrooz; de Aguiar, Sara R. M. M.; Stöger, Berthold; Widhalm, Michael; Kirchner, Karl; ChemCatChem; vol. 9; nb. 10; (2017); p. 1744 - 1748 View in Reaxys 2.1. Representative procedure for transfer hydrogenation reaction ofacetophenone General procedure: To a solution of acetophenone (58 μL, 0.5 mmol) in 2-propanol (0.5 mL) was added a stock solution of manganese pentacarbonyl bromide (0.5 mL, 0.005 mol·L−1; 2.7 mg, 0.010 mmol, in 2 mL 2-propanol)followed, in this order, by a stock solution of ethylenediamine (0.5 mL,0.005 mol·L−1; 1.0 μL, 0.0125 mmol, in 2.5 mL 2-propanol) and tBuOK (0.5 mL, 0.010 mol·L−1; 2.4 mg, 0.020 mmol, in 2 mL 2-propanol). The reaction mixture was stirred for 3 h at 80 °C in an oil bath. The solution was then filtered through a small pad of silica (2 cm in a Pasteur pip-ette). The silica was washed with ethyl acetate. The filtrate was evaporated and the conversion was determined by 1H NMR. The crude residue was then puried by column chromatography (SiO 2 , mixture of petroleum ether/ethyl acetate or dietyl ether as eluent. Enantiomeric excesses were determined by GC analyses performedon GC-2014 (Shimadzu) 2010 apparatus equipped with Supelco beta-DEX 120 column (30 m × 0.25 mm). The determination of the absoluteconguration was done by comparison with (S)-alcohol obtained bykinetic resolution of racemic alcohols with Novozym 435 (CandidaAntarctica Lipase B) and by comparison of the retention times with the literature [32–34]. With bromopentacarbonylmanganese(I), potassium tert-butylate, (1R,2R)-(+)-N,N'-dimethyl-1,2-diphenyl-ethylenediamine in isopropyl alcohol, Time= 3h, T= 80 °C , enantioselective reaction Wang, Ding; Bruneau-Voisine, Antoine; Sortais, Jean-Baptiste; Catalysis Communications; vol. 105; (2018); p. 31 - 36 View in Reaxys With NADP, alcohol dehydrogenase, Enzymatic reaction, stereoselective reaction Qu, Ge; Lonsdale, Richard; Yao, Peiyuan; Li, Guangyue; Liu, Beibei; Reetz, Manfred T.; Sun, Zhoutong; ChemBioChem; vol. 19; nb. 3; (2018); p. 239 - 246 View in Reaxys With C35H40BrFeN2OP2 (1+)*C24H20B(1-), potassium tert-butylate, isopropyl alcohol, Time= 0.05h, T= 28 °C , Catalytic behavior, enantioselective reaction Smith, Samantha A. M.; Prokopchuk, Demyan E.; Morris, Robert H.; Israel Journal of Chemistry; vol. 57; nb. 12; (2017); p. 1204 - 1215 View in Reaxys With C34H40ClIrN3 (1+)*F6P(1-), potassium tert-butylate, hydrogen in tetrahydrofuran, Time= 2h, T= 50 °C , p= 18751.9Torr , Inert atmosphere, Catalytic behavior, Reagent/catalyst Wan, Kai Y.; Roelfes, Florian; Lough, Alan J.; Hahn, F. Ekkehardt; Morris, Robert H.; Organometallics; vol. 37; nb. 3; (2018); p. 491 - 504 View in Reaxys With LIVTQTMKGLDIQKVAGTWYSLAMAASDISLLDAQSAPLRVYVEELKPTPEGDLEILLQKWENDECAQKKIIAEKTKIPAVFKIDALNENKVLVLDTDYKKYLLFCMENSAEPEQSLVCQCLVRTPEVDDEALEKFDKALKALPMHIRLSFNPTQLEEQC, [Ru(η6-benzene)(μ-Cl)Cl]2, sodium formate, Time= 40h, T= 40 °C , pH= 7.5, Green chemistry, Enzymatic reaction, Catalytic behavior, Kinetics, enantioselective reaction

169/258

2018-07-03 17:29:03

de Jesús Cázares-Marinero, José; Przybylski, Cédric; Salmain, Michèle; European Journal of Inorganic Chemistry; vol. 2018; nb. 12; (2018); p. 1383 - 1393 View in Reaxys With (CH3C6H4CH(CH3)2)RuCl(NH2CH(C6H5)CH(C6H5)NSO2C6F5), sodium formate in 2,2,2-trifluoroethanol, water, Time= 24h, T= 50 °C , enantioselective reaction Liu, Huan; Liu, Sensheng; Zhou, Haifeng; Liu, Qixing; Wang, Chunqin; RSC Advances; vol. 8; nb. 27; (2018); p. 14829 14832 View in Reaxys

H HO

Rx-ID: 8811903 View in Reaxys 5/176 Yield 59 %

Conditions & References With Arthrobacter atrocyaneus in N,N-dimethyl-formamide, Time= 48h, T= 32 °C , Microbiological reaction, enantioselective reaction Silva, Camila R.; Souza, Juliana C.; Araujo, Lidiane S.; Kagohara, Edna; Garcia, Thais P.; Pelizzari, Vivian H.; Andrade, Leandro H.; Journal of Molecular Catalysis B: Enzymatic; vol. 83; (2012); p. 23 - 28 View in Reaxys

58 %

With palladium dichloro (η-2,5-norbornadiene), oxygen, (-)-sparteine in toluene, Time= 192h, T= 80 °C , Title compound not separated from byproducts Ferreira; Stoltz; Journal of the American Chemical Society; vol. 123; nb. 31; (2001); p. 7725 - 7726 View in Reaxys

58 %

With 3 A molecular sieve, oxygen, (-)-sparteine, palladium dichloro (η-2,5-norbornadiene) in toluene, Time= 192h, T= 80 °C , p= 760Torr Ferreira; Stoltz; Journal of the American Chemical Society; vol. 123; nb. 31; (2001); p. 7725 - 7726 View in Reaxys With immobilized ovalbumin in water, Time= 144h, T= 35 °C , Title compound not separated from byproducts Nagaoka; Kayahara; Wakabayashi; Bioscience, biotechnology, and biochemistry; vol. 65; nb. 3; (2001); p. 634 - 637 View in Reaxys With immobilized pea protein in water, Time= 168h, T= 35 °C , Title compound not separated from byproducts Nagaoka; Kayahara; Wakabayashi; Bioscience, biotechnology, and biochemistry; vol. 65; nb. 3; (2001); p. 634 - 637 View in Reaxys With dichloro bis(acetonitrile) palladium(II), (-)-sparteine in 1,2-dichloro-ethane, T= 70 °C Jensen; Pugsley; Sigman; Journal of the American Chemical Society; vol. 123; nb. 30; (2001); p. 7475 - 7476 View in Reaxys With dichloro bis(acetonitrile) palladium(II), oxygen, (-)-sparteine in 1,2-dichloro-ethane, T= 70 °C , Title compound not separated from byproducts Jensen; Pugsley; Sigman; Journal of the American Chemical Society; vol. 123; nb. 30; (2001); p. 7475 - 7476 View in Reaxys With lyophilized cells of Rhodococcus ruber DSM 44541, acetone in phosphate buffer, Time= 24h, T= 24 °C , pH= 8.0, Title compound not separated from byproducts

170/258

2018-07-03 17:29:03

Stampfer, Wolfgang; Kosjek, Birgit; Faber, Kurt; Kroutil, Wolfgang; Journal of Organic Chemistry; vol. 68; nb. 2; (2003); p. 402 - 406 View in Reaxys With sodium isopropylate, acetone, [RuCl2(PPh3)(ferrocenyloxazolinylphosphine)] in isopropyl alcohol, Time= 0.5h, T= 50 °C Nishibayashi, Yoshiaki; Yamauchi, Akiyoshi; Onodera, Gen; Uemura, Sakae; Journal of Organic Chemistry; vol. 68; nb. 15; (2003); p. 5875 - 5880 View in Reaxys With 3 A molecular sieve, oxygen, sodium carbonate, Pd((-)-sparteine)2Cl2 in tert-butyl alcohol, Time= 24h, T= 65 °C , Title compound not separated from byproducts Mandal, Sunil K.; Sigman, Matthew S.; Journal of Organic Chemistry; vol. 68; nb. 19; (2003); p. 7535 - 7537 View in Reaxys Stage 1: With MnIII(L-5-t-Bu)(Cl), 1-butyl-2,6-dimethyl-pyridinium; bromide in dichloromethane, water, T= 20 °C Stage 2: With [bis(acetoxy)iodo]benzene in dichloromethane, water, Time= 0.1h, T= 20 °C Cheng, Qigan; Deng, Fanguo; Xia, Chungu; Sun, Wei; Tetrahedron Asymmetry; vol. 19; nb. 20; (2008); p. 2359 - 2362 View in Reaxys With (1R,2S,9S)-11-methyl-13-oxa-7,11-diazatricyclo[7.3.1.02,7]tridecane, C11H20Br2N2OPd, oxygen, caesium carbonate in chloroform, Time= 60h, T= 20 °C , Molecular sieve, optical yield given as percent ee Breuning, Matthias; Steiner, Melanie; Mehler, Christian; Paasche, Alexander; Hein, David; Journal of Organic Chemistry; vol. 74; nb. 3; (2009); p. 1407 - 1410 View in Reaxys With η-naphthol, C136H102Fe2N4O6 in toluene, Time= 40h, T= 50 °C , optical yield given as percent ee Kunisu, Takashi; Oguma, Takuya; Katsuki, Tsutomu; Journal of the American Chemical Society; vol. 133; nb. 33; (2011); p. 12937 - 12939 View in Reaxys Stage 1: With Br(1-)*C75H107Cl2Mn2N8O4 (1+), potassium bromide in dichloromethane, water, Time= 0.166667h, T= 20 °C Stage 2: With [bis(acetoxy)iodo]benzene in dichloromethane, water, optical yield given as percent ee Li, Chengyong; Zhao, Jiangfeng; Tan, Rong; Peng, Zhigang; Luo, Rongchang; Peng, Ming; Yin, Donghong; Catalysis Communications; vol. 15; nb. 1; (2011); p. 27 - 31 View in Reaxys With bis(1,5-cyclooctadiene)diiridium(I) dichloride, cetyltrimethylammonim bromide, acetone, potassium hydroxide, N,N'bis[o-(diphenylphosphino)benzylidene]-(1S,2S)-diaiminocyclohexane in water, Time= 16h, T= 28 °C , Resolution of racemate, Inert atmosphere, optical yield given as percent ee, enantioselective reaction Zhang, Juanni; Yang, Xiangren; Zhou, Han; Li, Yanyun; Dong, Zhenrong; Gao, Jingxing; Green Chemistry; vol. 14; nb. 5; (2012); p. 1289 - 1292 View in Reaxys 2.5. Typical procedure for the OKR of racemic secondary alcohols General procedure: Racemic secondary alcohols (0.25 mmol), catalyst (1.5 molpercent of substrate), and KBr (0.02 mmol, 0.0024 g) were added to H2O(1.5 mL). The mixture was stirred for 10 min at room temperature, and then PhI(OAc)2 (0.175 mmol, 0.056 g) was added in four equal parts. The reaction progress was monitored by gas chromatography (GC). After achieving the desired oxidation level, the reaction mixture was heated to 40 ηC. The catalyst was precipitated out of the reaction system, washed with diethyl ether(3× 5 mL), dried in a vacuum, and finally recharged with fresh substrate, additive, and oxidant for the next catalytic cycle. The supernatants separated from the reaction system were extractedwith ether three times. The collected organic phase was driedover sodium sulfate and concentrated in a vacuum. The resultantmixture was purified by column chromatography on silica gel athe stationary phase (petroleum ether/ethyl acetate, 90/10). Enantioselectivitywas determined by a Agilent Technologies 6890NGC system equipped with a 19091G-B213 chiral capillary column(30 m×0.32 mm×0.25 m) with an FID. Stage 1: With potassium bromide in water, Time= 0.166667h, T= 25 °C , Resolution of racemate Stage 2: With [bis(acetoxy)iodo]benzene in water, Time= 2h, T= 25 °C , enantioselective reaction

171/258

2018-07-03 17:29:03

Tan, Rong; Dong, Yan; Peng, Ming; Zheng, Weiguo; Yin, Donghong; Applied Catalysis A: General; vol. 458; (2013); p. 1 10 View in Reaxys Typical procedure for the OKR of racemic secondary alcohols with C2-PhI(OAc)2 system General procedure: Typical procedure for the OKR of racemic secondary alcohols with C2-PhI(OAc)2 system To a 5 mL glass reactor substrate (0.25 mmol), catalyst C2 (0.005 mmol, 2 molpercent), CH2Cl2 (0.3 mL) and H2O (0.6 mL) were added and the resulting mass was magnetically stirred for 5 min. To the above stirring mass, KBr (4 molpercent) was added at room temperature. The reaction mixture was then cooled to 15 °C and PhI(OAc)2 (0.7 equiv.) was added slowly in small fractions over 15 min and stirring was continued to the specified time. After the completion of the reaction, catalyst was precipitated out by the addition of hexane to the reaction mixture. The recovered catalyst was dried and stored for future use. An aliquot of organic layer was subjected to HPLC analysis to determine enantiomeric excess (ee) of the product. The resulting ketone and enantio-enriched secondary alcohol were separated by silica gel flash chromatography. With [bis(acetoxy)iodo]benzene, C36H50ClMnN2O6, potassium bromide in dichloromethane, water, Time= 0.5h, T= 15 °C Bera, Prasanta Kumar; Maity, Nabin Ch.; Abdi, Sayed H.R.; Khan, Noor-Ul H.; Kureshy, Rukhsana I.; Bajaj, Hari C.; Applied Catalysis A: General; vol. 467; (2013); p. 542 - 551 View in Reaxys 2.2. Catalytic procedure. General procedure: In a typical process, a mixture of (±)-1-phenylethanol (0.122 g, 1 mmol), chiral Mn(III)-salen complex (0.0127 g, 2 molpercent), Br2 (4.1 μL, 8 molpercent), KOAC (0.1962 g, 2 mmol), CH2Cl2 (2.0 mL), and water (4.0 mL) was magnetically stirred in a 10-mL two-necked flask at 20 °C. The oxidant NaClO (0.289 g, 0.80 mmol) was then added slowly within 40 min, and the reaction was monitored by GC/HPLC equipped with a suitable chiral column. With sodium hypochlorite, C38H56ClMnN2O2, bromine, potassium acetate in dichloromethane, water, Time= 0.666667h, T= 20 °C , Kinetics, Mechanism, enantioselective reaction Zhang, Yuecheng; Zhou, Qiao; Ma, Wenchan; Zhao, Jiquan; Catalysis Communications; vol. 45; (2014); p. 114 - 117 View in Reaxys With lyophilised cells of Escherichia coli overexpressing the solvent-tolerant alcohol dehydrogenase from Rhodococcus ruber DSM44541 in aq. buffer, Time= 24h, T= 30 °C , pH= 7.5, Resolution of racemate, Enzymatic reaction Paul, Caroline E.; Lavandera, Ivan; Gotor-Fernandez, Vicente; Kroutil, Wolfgang; Gotor, Vicente; ChemCatChem; vol. 5; nb. 12; (2013); p. 3875 - 3881 View in Reaxys With (R,R)-1,2-di(1-naphthyl)-1,2-ethanediamine, tert.-butylhydroperoxide, potassium carbonate in water, acetonitrile, Time= 5h, T= 29 °C , Molecular sieve Al-Hunaiti, Afnan; Räisänen, Minna; Pihko, Petri; Leskelä, Markku; Repo, Timo; European Journal of Organic Chemistry; vol. 2014; nb. 28; (2014); p. 6141 - 6144 View in Reaxys With NADP in acetone, Time= 22h, T= 50 °C , pH= 8, Resolution of racemate Popłoński, Jarosław; Reiter, Tamara; Kroutil, Wolfgang; ChemCatChem; vol. 10; nb. 4; (2018); p. 763 - 768 View in Reaxys

172/258

2018-07-03 17:29:03

H HO

Rx-ID: 30065972 View in Reaxys 6/176 Yield

Conditions & References Stage 1: With (S,R(P))-2-phenyl-2,3-dihydroimidazo[1,2-a]pyrindinyl-pentaphenylcyclopentadienyliron, N-ethyl-N,N-diisopropylamine in toluene, Time= 0.0833333h, T= 0 °C Stage 2: in toluene, Time= 7h, T= 0 °C , optical yield given as percent ee, enantioselective reaction Hu, Bin; Meng, Meng; Wang, Zheng; Du, Wenting; Fossey, John S.; Hu, Xinquan; Deng, Wei-Ping; Journal of the American Chemical Society; vol. 132; nb. 47; (2010); p. 17041 - 17044 View in Reaxys With N-ethyl-N,N-diisopropylamine in chloroform, Time= 7h, T= 0 °C , enantioselective reaction Neyyappadath, Rifahath Mon; Chisholm, Ross; Greenhalgh, Mark D.; Rodríguez-Escrich, Carles; Pericàs, Miquel A.; Hähner, Georg; Smith, Andrew D.; ACS Catalysis; vol. 8; nb. 2; (2018); p. 1067 - 1075 View in Reaxys HO

H HO

Rx-ID: 46997871 View in Reaxys 7/176 Yield

Conditions & References 4.2. General procedure for the kinetic resolution of secondaryalcohols by catalytic benzoylation General procedure: A two-neck round-bottom flask containing powdered 4Å molecular sieves (0.6 g) was dried under nitrogen atmosphere. A solution of secondary alcohol (3 mmol) in CHCl3 (6 mL) was added to the flask. Subsequently, catalyst 2 (108 mg, 0.3 mmol) and i-Pr2NEt (233 mg, 1.8 mmol) were added to the solution, and benzoyl chloride (253 mg, 1.8 mmol) was added dropwise to the mixture at 0°C. After the resulting mixture was stirred at 0°C for 5h, the molecular sieves were filtered with suction filtration. To the filtrate, water was added, and the mixture was extracted with CHCl3. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated under reduced pressure. The crude reaction mixture was purified by flash column chromatography using a mixture of ethyl acetate/n-hexane, affording the corresponding benzoate and recovering the alcohol. With C23H24NOP, N-ethyl-N,N-diisopropylamine in chloroform, Time= 5h, T= 0 °C , Inert atmosphere, Molecular sieve, stereoselective reaction Hara, Nanami; Fujisawa, Shu; Fujita, Mizuki; Miyazawa, Mikako; Ochiai, Kazuma; Katsuda, Satoshi; Fujimoto, Tetsuya; Tetrahedron; vol. 74; nb. 2; (2018); p. 296 - 302 View in Reaxys

173/258

2018-07-03 17:29:03

O OH

Rx-ID: 47194689 View in Reaxys 8/176 Yield

Conditions & References With Amano lipase PS from Burkholderia cepacia immobilized on covalent organic framework in hexane, Time= 0.5h, T= 45 °C , Resolution of racemate, Overall yield = 48 percent Sun, Qi; Fu, Chung-Wei; Aguila, Briana; Perman, Jason; Wang, Sai; Huang, Hsi-Ya; Xiao, Feng-Shou; Ma, Shengqian; Journal of the American Chemical Society; vol. 140; nb. 3; (2018); p. 984 - 992 View in Reaxys

O HO

H O

Rx-ID: 47397271 View in Reaxys 9/176 Yield

Conditions & References With subtilisin Carlsberg G165L/M221F immobilized on Accurel MP1000, sodium carbonate in tetrahydrofuran, Time= 48h, T= 23 °C , Inert atmosphere, Enzymatic reaction, Catalytic behavior, Reagent/catalyst, enantioselective reaction Dorau, Robin; Görbe, Tamás; Svedendahl Humble, Maria; ChemBioChem; vol. 19; nb. 4; (2018); p. 338 - 346 View in Reaxys

H HO

Rx-ID: 47837879 View in Reaxys 10/176 Yield

Conditions & References Reaction Steps: 2 1: trifluorormethanesulfonic acid; water / 2,2,2-trifluoroethanol / 48 h / 40 °C 2: (CH3C6H4CH(CH3)2)RuCl(NH2CH(C6H5)CH(C6H5)NSO2C6F5); sodium formate / 2,2,2-trifluoroethanol; water / 24 h / 50 °C With trifluorormethanesulfonic acid, (CH3C6H4CH(CH3)2)RuCl(NH2CH(C6H5)CH(C6H5)NSO2C6F5), water, sodium formate in 2,2,2-trifluoroethanol, water Liu, Huan; Liu, Sensheng; Zhou, Haifeng; Liu, Qixing; Wang, Chunqin; RSC Advances; vol. 8; nb. 27; (2018); p. 14829 14832 View in Reaxys

H HO

Rx-ID: 8874752 View in Reaxys 11/176

174/258

2018-07-03 17:29:03

Yield

Conditions & References With (1S,2R)-(+)-N,N-dimethylephedrinium bis(trifluoromethanesulfon)imidate in dichloromethane, T= 120 °C Ding, Jie; Welton, Thomas; Armstrong, Daniel W.; Analytical Chemistry; vol. 76; nb. 22; (2004); p. 6819 - 6822 View in Reaxys Stage 1: With (R,R)-1,2-diphenylethylenediamine, cyclohexanone, (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl, [Ru(PPh3)4H2] in tetrahydrofuran, Time= 4h, T= 60 °C Stage 2: With hydrogen in tetrahydrofuran, Time= 16h, T= 40 °C , p= 7500.6Torr , Title compound not separated from byproducts Adair, Gareth R. A.; Williams, Jonathan M. J.; Chemical Communications; nb. 44; (2005); p. 5578 - 5579 View in Reaxys Stage 1: With Candida antarctica lipase B, vinyl acetate in toluene, T= 20 °C Stage 2: With dmap, polymer-bound benzoyl chloride, triethylamine in dichloromethane, T= 20 °C Stage 3: With potassium hydroxide in tetrahydrofuran, methanol, Time= 12h, Further stages. Title compound not separated from byproducts. Cordova; Tremblay; Clapham; Janda; Journal of Organic Chemistry; vol. 66; nb. 16; (2001); p. 5645 - 5648 View in Reaxys With (3R,4S)-4-(3,5-dinitrobenzamido)-1,2,3,4-tetrahydrophenanthren-3-yl covalently linked to 3-propyl silica surface in hexane, acetic acid, isopropyl alcohol, T= 25 °C , pH= 3.6, Resolution of racemate Aneja, Ritu; Luthra, Pratibha Mehta; Ahuja, Satinder; Chirality; vol. 22; nb. 5; (2010); p. 479 - 485 View in Reaxys With (R)-(-)-benzotetramisole, 2,4,6-trimethyl-benzoic acid-anhydride, N-ethyl-N,N-diisopropylamine, 3-Phenylpropionic acid in dichloromethane, Time= 12h, T= 20 °C , optical yield given as percent ee, enantioselective reaction Shiina, Isamu; Nakata, Kenya; Sugimoto, Masuhiro; Onda, Yu-Suke; Iizumi, Takashi; Ono, Keisuke; Heterocycles; vol. 77; nb. 2; (2009); p. 801 - 810 View in Reaxys With C9H8N2*C18H14O8 in water, acetonitrile, T= 20 °C , Resolution of racemate, optical yield given as percent ee, enantioselective reaction Kodama, Koichi; Sekine, Eriko; Hirose, Takuji; Chemistry - A European Journal; vol. 17; nb. 41; (2011); p. 11527 - 11534 View in Reaxys With C13H14N2*C18H14O8 in water, acetonitrile, T= 20 °C , Resolution of racemate, optical yield given as percent ee, enantioselective reaction Kodama, Koichi; Sekine, Eriko; Hirose, Takuji; Chemistry - A European Journal; vol. 17; nb. 41; (2011); p. 11527 - 11534 View in Reaxys With C14H15NO8Zn2, Time= 48h, Resolution of racemate, optical yield given as percent ee Suh, Kyungwon; Yutkin, Maxim P.; Dybtsev, Danil N.; Fedin, Vladimir P.; Kim, Kimoon; Chemical Communications; vol. 48; nb. 4; (2012); p. 513 - 515 View in Reaxys With tetraproline chiral stationary phase packed on HPLC column in hexane, isopropyl alcohol, Resolution of racemate Dai, Zhi; Ye, Guozhong; Pittman Jr., Charles U.; Li, Tingyu; Chirality; vol. 24; nb. 4; (2012); p. 329 - 338 View in Reaxys With C4H8O*C168H192Cl8N16O8Zn8*H2O in diethyl ether, optical yield given as percent ee Xuan, Weimin; Zhang, Mengni; Liu, Yan; Chen, Zhijie; Cui, Yong; Journal of the American Chemical Society; vol. 134; nb. 16; (2012); p. 6904 - 6907 View in Reaxys With {[Cd2(l-cps)4(1,4-bis(imidazol-1-yl-methyl)benzene)4]·(CH2Cl2)2(EtOH)(H2O)}n in chloroform, Time= 168h, T= -18 °C , enantioselective reaction

175/258

2018-07-03 17:29:03

Li, Zi-Jian; Yao, Jia; Tao, Qian; Jiang, Long; Lu, Tong-Bu; Inorganic Chemistry; vol. 52; nb. 20; (2013); p. 11694 - 11696 View in Reaxys Reaction Steps: 2 1: methanol / 80 °C 2: methanol / 72 h / 40 °C in methanol Lin, Lang; Yu, Rongmin; Wu, Xiao-Yuan; Yang, Wen-Bin; Zhang, Jian; Guo, Xiang-Guang; Lin, Zu-Jin; Lu, CanZhong; Inorganic Chemistry; vol. 53; nb. 10; (2014); p. 4794 - 4796 View in Reaxys Time= 30h, T= 150 °C , Resolution of racemate Dong, Jinqiao; Liu, Yan; Cui, Yong; Chemical Communications; vol. 50; nb. 95; (2014); p. 14949 - 14952 View in Reaxys With sodium hypochlorite, N-Bromosuccinimide, [(R,Rη)-N,Nη-bis(3,5-di-tertbutylsalicylidene)-1,2-cyclohexanediaminato]manganese(III) chloride, water, potassium acetate in dichloromethane, Time= 1h, T= 20 °C , Resolution of racemate, Green chemistry, Kinetics, Optical yield = 10.8 percent ee; enantioselective reaction Zhang, Yuecheng; Gao, Baosheng; Zhou, Qiao; Zhao, Jiquan; Catalysis Letters; vol. 144; nb. 11; (2014); p. 1797 - 1802 View in Reaxys Screening procedure General procedure: Erlenmeyer flasks (300 ml), each containing 100 ml of the medium consisting of 3 g glucose and 1 g aminobac dissolved in water,were inoculated with a suspension of microorganisms and then incubated for 3–7 days at 25 C on a rotary shaker (190 rpm). After full growth of the culture 20 mg of a substrate dissolved in 1 ml of acetone was added. After 1, 3, 6, 9, 12 h and 1, 3, 6, 9 days of incubation under the above conditions, portions of 5 ml of the transformation mixture were taken out and extracted with CHCl3(3*10 ml). The extracts were dried over MgSO4, concentrated in vacuo, and analyzed by GC. All the experiments were repeatedthree times. With yeast culture of Yarrowia lipolytica KCh 71 in acetone, Time= 216h, T= 25 °C , Microbiological reaction, Reagent/catalyst, Overall yield = 97 percentChromat.; enantioselective reaction Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys With chiral poly(phenylacetylene)polymer coated on aminopropyl silanized silica gel in hexane, isopropyl alcohol, Resolution of racemate, Reagent/catalyst Zhang, Chunhong; Ma, Rui; Wang, Hailun; Sakai, Ryosuke; Satoh, Toshifumi; Kakuchi, Toyoji; Liu, Lijia; Okamoto, Yoshio; Chirality; vol. 27; nb. 8; (2015); p. 500 - 506 View in Reaxys With [Co2(S-mandelate)2(4,4'-bipyridine)3](NO3)2*dichloromethane, Time= 168h, T= 20 °C , Resolution of racemate, Catalytic behavior, Time, Reagent/catalyst, enantioselective reaction Zhang, Shi Yuan; Wojtas, Lukasz; Zaworotko, Michael J.; Journal of the American Chemical Society; vol. 137; nb. 37; (2015); p. 12045 - 12049 View in Reaxys With [Co2(R-mandelate)2(4,4'-bipyridine)3](NO3)2*dichloromethane, Time= 168h, T= 20 °C , Resolution of racemate, Catalytic behavior, Time, Reagent/catalyst, enantioselective reaction Zhang, Shi Yuan; Wojtas, Lukasz; Zaworotko, Michael J.; Journal of the American Chemical Society; vol. 137; nb. 37; (2015); p. 12045 - 12049 View in Reaxys With Cu-(R)-2,2'-dihydroxy-1,1'-binaphthalene-6,6'-dicarboxylic acid organic framework silica composite in hexane, dichloromethane, Resolution of racemate Tanaka, Koichi; Muraoka, Toshihide; Otubo, Yasuhiro; Takahashi, Hiroki; Ohnishi, Atsushi; RSC Advances; vol. 6; nb. 26; (2016); p. 21293 - 21301 View in Reaxys

176/258

2018-07-03 17:29:03

With pentyl cage-coated capillary column, Resolution of racemate Xie, Shengming; Zhang, Junhui; Fu, Nan; Wang, Bangjin; Hu, Cong; Yuan, Liming; Molecules; vol. 21; nb. 11; (2016); Art.No: 1466 View in Reaxys With {[CuI 2CuII((1S)-1-(5-tetrazolyl)ethylamine)2(CN-)(H2O)]+[NO3 -]}*[DMF] in methanol, water, Time= 72h, T= 20 °C , Resolution of racemate, Solvent, enantioselective reaction Liu, Juan; Wang, Fei; Ding, Qing-Rong; Zhang, Jian; Inorganic Chemistry; vol. 55; nb. 24; (2016); p. 12520 - 12522 View in Reaxys General procedure: Gas chromatographicmeasurements were performed on a GC-14B (Shimadzu, Japan) system withflame ionization detector. Nitrogen (99.999percent) was used as the carrier gas. Aη-DEX 225 capillary column (30 m long × 0.25 mm i.d. × 0.25 μm filmthickness, Supelco Inc.), a Chirasil L-Val capillary column (25 m long × 0.25mm i.d. × 0.12 μm film thickness, Agilent Technologies), and a Cyclosil-Bcapillary column (30 m long × 0.32 mm i.d. × 0.25 μm film thickness, AgilentTechnologies) were employed as commercial columns for comparison. With [Co2((S)-mandelate)2(4,4'-bipyridine)3](NO3)2 coated capillary column, Time= 0.0283333h, T= 150 °C , Resolution of racemate, Reagent/catalyst Zhang, Shi-Yuan; Yang, Cheng-Xiong; Shi, Wei; Yan, Xiu-Ping; Cheng, Peng; Wojtas, Lukasz; Zaworotko, Michael J.; Chem; vol. 3; nb. 2; (2017); p. 281 - 289 View in Reaxys

H OH

Rx-ID: 8940491 View in Reaxys 12/176 Yield 90 % Chromat., 8 % Chromat.

Conditions & References With Sphingomonas paucimobilis NCIMB 8195 in water, N,N-dimethyl-formamide, Time= 120h Allan; Carnell; Journal of Organic Chemistry; vol. 66; nb. 19; (2001); p. 6495 - 6497 View in Reaxys 3 :An 8 ml glass vial was charged with 1.2mg peptoid (7mers, lxlηηnol), 0.25 ml CH2Cl2, 0.125 ml of 0.5M KBr in water and lxlηηnol substrate (alcohol), placed in an ice bath and cooled to 0°C under stirring. The reaction started with the addition of 0.310 ml 0.5M NaOCl solution [1 equivalent of 1.8M NaOCl (that contains 10-13percent Cl) and 2.6 equivalents of water]. After two hours, 1 ml CH2Cl2 was added, the aqueous layer was separated and a sample from the CH2Cl2 solution was analyzed by GC. With sodium hypochlorite, potassium bromide, H-NtempoNspeNpm(Nspe)2NpmNspe-NH2 in dichloromethane, water, Time= 2h, T= 0 °C , Product distribution / selectivity Patent; NEW YORK UNIVERSITY SCHOOL OF MEDICINE; WO2009/139922; (2009); (A2) English View in Reaxys Typical procedure for the OKR of racemic secondary alcohols with C2-NBS system General procedure: Typical procedure for the OKR of racemic secondary alcohols with C2-NBS system To a 5 mL glass reactor substrate (0.25 mmol), catalyst C2 (0.0037 mmol, 1.5 molpercent), KOAc (0.8 equiv.), CH2Cl2 (0.5 mL) and H2O (1 mL) were added and the resulting mass was magnetically stirred for 5 min. To the stirring mass NBS (0.7 equiv.) was added slowly in small fractions over 20 min and stirring was continued for the specified time. After the completion of the reaction, catalyst was precipitated out by the addition of hexane to the reaction mixture. The recovered catalyst was dried and stored for further use. An aliquot of organic layer was subjected to HPLC analysis to determine enantiomeric excess (ee) of the product. The resulting ketone and enantio-enriched secondary alcohol were separated by silica gel flash chromatography. With N-Bromosuccinimide, C36H50ClMnN2O6, potassium acetate in dichloromethane, water, T= 20 °C Bera, Prasanta Kumar; Maity, Nabin Ch.; Abdi, Sayed H.R.; Khan, Noor-Ul H.; Kureshy, Rukhsana I.; Bajaj, Hari C.; Applied Catalysis A: General; vol. 467; (2013); p. 542 - 551

177/258

2018-07-03 17:29:03

View in Reaxys With (R,R)-1,2-di(1-naphthyl)-1,2-ethanediamine, tert.-butylhydroperoxide, potassium carbonate in decane, dichloromethane, Time= 20h, T= 29 °C , Molecular sieve Al-Hunaiti, Afnan; Räisänen, Minna; Pihko, Petri; Leskelä, Markku; Repo, Timo; European Journal of Organic Chemistry; vol. 2014; nb. 28; (2014); p. 6141 - 6144 View in Reaxys With Fusarium proliferatum mycelia in aq. phosphate buffer, pH= 7.2, Microbiological reaction, Resolution of racemate, enantioselective reaction Jadhav, Dipesh D.; Patil, Harshal S.; Chaya, Patil S.; Thulasiram, Hirekodathakallu V.; Tetrahedron Letters; vol. 57; nb. 41; (2016); p. 4563 - 4567 View in Reaxys With sulfuric acid, MnII((1R,2R)-N,N'-dimethyl-N,N'-bis((R)-(3,5-di-tert-butylphenyl)-2-pyridinylmethyl)cyclohexane-1,2-diamine)(OTf)2, dihydrogen peroxide in water, acetonitrile, Time= 1h, T= 0 °C , Inert atmosphere, Schlenk technique Miao, Chengxia; Li, Xiao-Xi; Lee, Yong-Min; Xia, Chungu; Wang, Yong; Nam, Wonwoo; Sun, Wei; Chemical Science; vol. 8; nb. 11; (2017); p. 7476 - 7482 View in Reaxys

H HO

Rx-ID: 39087131 View in Reaxys 13/176 Yield 66 %

Conditions & References 2.3. General procedure for the 1-phenyl-2-propene-1-ol allylic isomerization in THF General procedure: A solution containing 6.4 × 10−3mmol of precatalyst and0.13 mmol of substrate (20 equiv.) in 2 mL of THF was transferred into a 5 mL glass vial which was then placed under argon into a stainless steel autoclave equipped with a magnetic stirring bar. The reaction vessel was pressurized with H2 to 30 bar and stirred for the desired time at room temperature. Then pressure was released andthe reaction vessel was stirred for the desired time at controlledtemperature under a dihydrogen atmosphere at 1 bar. Alterna-tively, after venting the H2pressure used for the catalyst activation,the residual H2was purged with argon by continuous flushingbefore continuing the reaction. The pure products were obtainedby chromatography of the reaction mixture on silica gel using dichloromethane as eluent and then analyzed by NMR spectrosopyand chiral GC for the determination of the yields and enantiomeric excesses. With C34H41ClFePRhS, hydrogen, sodium methylate in tetrahydrofuran, Time= 16h, T= 82 °C , p= 22502.3Torr , Autoclave, Inert atmosphere Titova, Ekaterina M.; Rahaman, S.M. Wahidur; Shubina, Elena S.; Poli, Rinaldo; Belkova, Natalia V.; Manoury, Eric; Journal of Molecular Catalysis A: Chemical; vol. 426; (2017); p. 376 - 380 View in Reaxys With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, potassium tert-butylate, lithium chloride, t-butyl [(S)-1-((S)-2-hydroxypropylcarbamoyl)ethyl]carbamate in tetrahydrofuran, ethanol, Time= 3h, T= 40 °C , Inert atmosphere, Concentration, enantioselective reaction Slagbrand, Tove; Lundberg, Helena; Adolfsson, Hans; Chemistry - A European Journal; vol. 20; nb. 49; (2014); p. 16102 16106 View in Reaxys

178/258

2018-07-03 17:29:03

H HO

Rx-ID: 46594807 View in Reaxys 14/176 Yield

Conditions & References With ferredoxin reductase, ferredoxin, P450 monooxygenase CYP101B1 from a Novosphingobium bacterium, H85F mutant, NADH, bovine liver catalase in aq. buffer, T= 30 °C , pH= 7.4, Enzymatic reaction, Kinetics, Reagent/catalyst, enantioselective reaction Sarkar, Md. Raihan; Lee, Joel H. Z.; Bell, Stephen G.; ChemBioChem; vol. 18; nb. 21; (2017); p. 2119 - 2128 View in Reaxys

H OH

Rx-ID: 46906670 View in Reaxys 15/176 Yield

Conditions & References With methanol, recombinant evolved peroxygenase from Agrocybe aegerita, oxygen in aq. phosphate buffer, Time= 70h, T= 30 °C , pH= 7, Irradiation, Enzymatic reaction, Catalytic behavior, Overall yield = 72 percentChromat. Zhang, Wuyuan; Burek, Bastien O.; Fernández-Fueyo, Elena; Alcalde, Miguel; Bloh, Jonathan Z.; Hollmann, Frank; Angewandte Chemie - International Edition; vol. 56; nb. 48; (2017); p. 15451 - 15455; Angew. Chem.; vol. 129; nb. 48; (2017); p. 15654 - 15658,5 View in Reaxys

H HO

Rx-ID: 4343307 View in Reaxys 16/176 Yield

Conditions & References With dihydrogen peroxide, Time= 5h, chloroperoxidase from Caldaromyces fumago, citrate buffer pH=5.0, Yield given. Yields of byproduct given. Title compound not separated from byproducts Zaks; Dodds; Journal of the American Chemical Society; vol. 117; nb. 42; (1995); p. 10419 - 10424 View in Reaxys With Bacillus megaterium, oxygen, Time= 17h, T= 30 °C , Microbiological reaction, Oxidation, hydroxylation, Title compound not separated from byproducts. Adam, Waldemar; Lukacs, Zoltan; Harmsen, Dag; Saha-Moeller, Chantu R.; Schreier, Peter; Journal of Organic Chemistry; vol. 65; nb. 3; (2000); p. 878 - 882 View in Reaxys With perfluorodecanoic acid, wild type cytochrome P450Bm3, oxygen, NADPH, bovine liver catalase in dimethyl sulfoxide, T= 30 °C , pH= 7.4, Enzymatic reaction, Reagent/catalyst, enantioselective reaction Munday, Samuel D.; Dezvarei, Shaghayegh; Bell, Stephen G.; ChemCatChem; vol. 8; nb. 17; (2016); p. 2789 - 2796 View in Reaxys

179/258

2018-07-03 17:29:03

H O

Rx-ID: 4731319 View in Reaxys 17/176 Yield

Conditions & References With titanium(IV) isopropylate, (R)-1,1'-Bi-2-naphthol in tetrahydrofuran, toluene, Time= 5h, T= 0 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Chan; Zhang; Yip; Journal of the American Chemical Society; vol. 119; nb. 17; (1997); p. 4080 - 4081 View in Reaxys Stage 1: With titanium(IV) isopropylate, η,η,η',η'-tetraphenyl-1,3-dioxolane-4,5-dimethanol in tetrahydrofuran, toluene, Time= 0.5h, T= 20 °C , activation Stage 2: in tetrahydrofuran, toluene, Time= 10h, T= 0 °C , Addition, Title compound not separated from byproducts Lu, Jui-Feng; You, Jing-Song; Gau, Han-Mou; Tetrahedron Asymmetry; vol. 11; nb. 12; (2000); p. 2531 - 2535 View in Reaxys Stage 1: With titanium(IV) isopropylate, (S)-4,4',6,6'-tetraperfluorooctyl-1,1'-binaphthyl-2,2'-diol in hexane, Time= 0.25h, T= 53 °C Stage 2: in hexane, Time= 0.5h, T= 53 °C , Title compound not separated from byproducts Tian, Yuan; Yang, Qing Chuan; Mak, Thomas C.W.; Chan, Kin Shing; Tetrahedron; vol. 58; nb. 20; (2002); p. 3951 - 3961 View in Reaxys Stage 1: With 1,4-diaza-bicyclo[2.2.2]octane in tetrahydrofuran Stage 2: With [(R)-1,1'-binaphthyl-2,2'-diyldioxy]{bis[(S)-(1-phenylethyl)]amino}phosphine, bis(acetylacetonate)nickel(II) in tetrahydrofuran, Time= 5h, T= 5 °C , Title compound not separated from byproducts Biswas, Kallolmay; Prieto, Oscar; Goldsmith, Paul J.; Woodward, Simon; Angewandte Chemie - International Edition; vol. 44; nb. 15; (2005); p. 2232 - 2234 View in Reaxys With bis(acetylacetonate)nickel(II), biarylidene di-O-isopropylidene-η-D-glucofuranose phosphite in tetrahydrofuran, Time= 1h, T= -20 °C , Title compound not separated from byproducts Mata, Yvette; Dieguez, Montserrat; Pamies, Oscar; Woodward, Simon; Journal of Organic Chemistry; vol. 71; nb. 21; (2006); p. 8159 - 8165 View in Reaxys With titanium(IV) isopropylate, (R,S)-2-OH-3,5-Cl2-C6H2-SO2-NH-CH(CH2Ph)-CH(Ph)OH in tetrahydrofuran, Time= 12h, T= 0 °C , Product distribution, Further Variations: Reagents You; Hsieh; Gau; Chemical Communications; nb. 17; (2001); p. 1546 - 1547 View in Reaxys With bis(acetylacetonate)nickel(II), C64H93NO8P2 in tetrahydrofuran, T= -20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Raluy, Eva; Dieguez, Montserrat; Pamies, Oscar; Tetrahedron Letters; vol. 50; nb. 31; (2009); p. 4495 - 4497 View in Reaxys Stage 1: With bis(acetylacetonate)nickel(II), C30H44NO7PSi2 in tetrahydrofuran, T= -20 °C , Inert atmosphere Stage 2: With hydrogenchloride in tetrahydrofuran, water, optical yield given as percent ee, enantioselective reaction Raluy, Eva; Dieguez, Montserrat; Pamies, Oscar; Tetrahedron Asymmetry; vol. 20; nb. 13; (2009); p. 1575 - 1579 View in Reaxys 4.3. General procedure for the Ni-catalyzed enantioselective 1,2-addition of trialkylaluminum reagents to aldehydes

180/258

2018-07-03 17:29:03

General procedure: At first, [Ni(acac)2] (2.4 mg, 9.32 μmol, 1 mol percent) and ligand (9.32 μmol, 1 mol percent) were stirred in dry THF (8 mL) under an argon atmosphere at -20 °C for 10 min. Neat aldehyde (1 mmol) was then added and trialkylaluminum (2 mmol) was added dropwise over 10 min. After the desired reaction time, the reaction was quenched with 2 M HCl (8 mL). The mixture was extracted with Et2O (10 mL). The organic layer was dried over MgSO4 and analyzed by GC.5a Stage 1: With bis(acetylacetonate)nickel(II), C41H61O8P in tetrahydrofuran, Time= 3h, T= -20 °C , Inert atmosphere Stage 2: With hydrogenchloride, water in tetrahydrofuran, Inert atmosphere, optical yield given as percent ee, enantioselective reaction Alegre, Sabina; Dieguez, Montserrat; Pmies, Oscar; Tetrahedron Asymmetry; vol. 22; nb. 8; (2011); p. 834 - 839 View in Reaxys With titanium(IV) isopropylate, (S)-5,5’-biquinoline-6,6’-diol in tetrahydrofuran, hexane, Time= 6h, T= 0 °C , Solvent, enantioselective reaction Chen, Qian; Ou, Jun; Chen, Guo-Shu; Liu, Tian-Hui; Xie, Bin; Liang, Hai-Bo; Xie, Li-Qiong; Chen, Yi-Xin; Chirality; vol. 26; nb. 5; (2014); p. 268 - 271 View in Reaxys With titanium(IV) isopropylate in tetrahydrofuran, T= 0 °C , Catalytic behavior, Reagent/catalyst, Temperature, Solvent, Overall yield = 98 percent Liu, Dacai; Ouyang, Kunbing; Yang, Nianfa; Tetrahedron; vol. 72; nb. 7; (2016); p. 1018 - 1023 View in Reaxys

H HO

Rx-ID: 8564625 View in Reaxys 18/176 Yield

Conditions & References With sodium sulfate, N-ethyl-N,N-diisopropylamine, (R)-(-)-benzotetramisole in chloroform, Time= 36h, T= 0 °C , Title compound not separated from byproducts Birman, Vladimir B.; Li, Ximin; Organic Letters; vol. 8; nb. 7; (2006); p. 1351 - 1354 View in Reaxys With (-)-diethyl[3-(2-phenylnaphyhyl)(4-pyridyl)]amine, triethylamine in toluene, Time= 8.4h, T= -78 °C , Acylation, resolution, Title compound not separated from byproducts. Spivey, Alan C.; Fekner, Tomasz; Spey, Sharon E.; Journal of Organic Chemistry; vol. 65; nb. 10; (2000); p. 3154 - 3159 View in Reaxys With C28H26N2O, triethylamine in tert-Amyl alcohol, Time= 6.5h, T= 0 °C , Inert atmosphere, Resolution of racemate, optical yield given as percent ee Crittall, Matthew R.; Rzepa, Henry S.; Carbery, David R.; Organic Letters; vol. 13; nb. 5; (2011); p. 1250 - 1253 View in Reaxys Procedure and Analytical Data. General Procedureforthe Acylative Kinetic Resolution of Carbinols: General procedure: To a solution of substrate 2a2t(0.100 mmol), Cs2CO3 (24.4 mg, 75.0mol) and catalyst1d(4.8 mg, 5.00mol) inEt2O (3.00 mL)was added isobutyric anhydride (12.4L, 75.0mol)at60 °C. The reaction mixture was stirred for 15 h at60 °C.MeOH (2 mL) was then added to destroy unreactedisobutyricanhydride and the mixture was stirredfor 30 minasit warmedto room temperature. The resulting solution was concentratedin vacuo. The resulting mixture was passed through a short padofsili-

181/258

2018-07-03 17:29:03

ca gel(eluent: hexane/Et2O=1/1, v/v) to give the esterproduct and the unreacted alcohol,which were directly analyzed by chiralHPLC. The enantiomeric ratio (er) and enantiomeric excess (ee) values ofthe ester and the unreacted alcoholwere obtained by HPLC analysis. The conversion (C) and sfactor (s)ofkinetic resolution were calculated asfollows:52sln1C1ee0ln1C1ee0ln1C1eeln1C1eekfastkslow2eeenantiomeric excess measuredfor the starting material3ee0enantiomeric excess measuredfor the product 4Ceeeeee0100conversion 5 With C69H72N2O2, caesium carbonate, Time= 15h, T= -60 °C , Inert atmosphere, Resolution of racemate Fujii, Kazuki; Mitsudo, Koichi; Mandai, Hiroki; Suga, Seiji; Bulletin of the Chemical Society of Japan; vol. 89; nb. 9; (2016); p. 1081 - 1092 View in Reaxys

H HO

Rx-ID: 10025559 View in Reaxys 19/176 Yield

Conditions & References With Candida antarctica lipase B, RuCl(CO2)(η5C5Ph5), potassium tert-butylate, sodium carbonate in tetrahydrofuran, toluene, Time= 17h, T= 20 °C

90 %

Martin-Matute, Belen; Edin, Michaela; Bogar, Krisztian; Kaynak, F. Betuel; Baeckvall, Jan-E.; Journal of the American Chemical Society; vol. 127; nb. 24; (2005); p. 8817 - 8825 View in Reaxys With lipase B from Candida antarctica in neat (no solvent), Time= 4h, Milling, Resolution of racemate, Enzymatic reaction, enantioselective reaction Hernández, José G.; Frings, Marcus; Bolm, Carsten; ChemCatChem; vol. 8; nb. 10; (2016); p. 1769 - 1772 View in Reaxys

H OH

Rx-ID: 22128244 View in Reaxys 20/176 Yield 80 %

Conditions & References With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer, N-(tert-butoxycarbonyl)-L-valine-(6-O-benzoyl-1-O-benzyl-5deoxy-2,3-O-isopropylidene-5-thioamido-η-D-mannofuranose), potassium tert-butylate, lithium chloride in tetrahydrofuran, ethanol, Time= 24h, T= 40 °C , enantioselective reaction Margalef, Jèssica; Slagbrand, Tove; Tinnis, Fredrik; Adolfsson, Hans; Diéguez, Montserrat; Pàmies, Oscar; Advanced Synthesis and Catalysis; vol. 358; nb. 24; (2016); p. 4006 - 4018 View in Reaxys Reaction Steps: 2 2: Raney nickel; diethyl ether / Hydrogenation With diethyl ether, nickel Duveen; Kenyon; Journal of the Chemical Society; (1939); p. 1697,1700 View in Reaxys Reaction Steps: 2 1: [Ru(η3:η3-C10H16)Cl(η2-O,O-CH3CO2)] / aq. phosphate buffer / 2.5 h / 50 °C / pH 7 / Sealed tube; Inert atmosphere 2: NADPH; ketoreductase P1-A04 / aq. phosphate buffer; isopropyl alcohol / 24 h / 30 °C / pH 7 / Enzymatic reaction With [Ru(η3:η3-C10H16)Cl(η2-O,O-CH3CO2)], ketoreductase P1-A04, NADPH in aq. phosphate buffer, isopropyl alcohol

182/258

2018-07-03 17:29:03

Ríos-Lombardía, Nicolás; Vidal, Cristian; Liardo, Elisa; Morís, Francisco; García-Álvarez, Joaquín; González-Sabín, Javier; Angewandte Chemie - International Edition; vol. 55; nb. 30; (2016); p. 8691 - 8695; Angew. Chem.; vol. 128; nb. 30; (2016); p. 8833 - 8837,5 View in Reaxys

H HO

Rx-ID: 24947330 View in Reaxys 21/176 Yield

Conditions & References 1 : Preparation of optically active 1-phenyl-1-propanol A mixture of (+-)-1-phenyl-1-propanol (40.9 g), tributyrin (99.8 g) and lipase P (15 g) was agitated at 35° C. for 502 hours, followed by filtering off lipase P and subjecting the residue to vacuum distillation to obtain S-(-)-1-phenyl-1-propanol (19.9 g). bp: 71.8° C./2.5 mmHg, [η]D 24.8 =-14.4° (neat). Further, a fraction of bp 101.3° C./2.6 mmHg was subjected to hydrolysis reaction in a conventional manner to obtain R-(+)-1phenyl-1-propanol (10.2 g). [η]D 24.7 =+25.8° (neat). Patent; Chisso Corporation; US5076947; (1991); (A) English View in Reaxys 8 :General procedure: (RC, SFe)-1-[2-(bis(3,5-dimethylphenyl)phosphino)ferrocenyl]N-(6-pyridyl-2-methyl)ethylamine (12.6 mg, 0.022 mmol), [Ir(COD)Cl2 (7.32 mg, 1 mmol)Was added to a 25 mL Schlenk reaction tube,Vacuum / nitrogen three times, 2 mL of anhydrous ethanol was purged with nitrogen, and the mixture was stirred at room temperature for 1 hour. Acetophenone (4.8 g, 40 mmol) was added to a 100 mL autoclave, Add 30 mLThe nitrogen-substituted absolute ethanol, Then, the reaction liquid is added into the reaction kettle,After replacing the hydrogen three times, the pressure was increased to 20 atm,The mixture was stirred at room temperature for 24 hours, TLC showed that the reaction was complete and the product was obtained as a pale yellow liquid (R)-1-phenylethanol 2.2 g in 90.9percent yield and 78percent ee. With C43H47ClFeIrN2P, potassium tert-butylate, hydrogen in ethanol, Time= 18h, T= 20 °C , p= 15201Torr , Autoclave, stereoselective reaction Patent; Fourth Military Medical University,People's Liberation Army; Chen, Weiping; Zhang, sheng Yong; cheng, sikun; li, xiaoye; Nie, Huifang; (10 pag.); CN103012498; (2016); (B) Chinese View in Reaxys With lithium aluminium tetrahydride, tert-Amyl alcohol, trans-(S,S)-[Fe(Ph2PCH(Ph)CH(Me)NCHCH2PCy2)(C0)2(Br)][BF4], potassium tert-butylate, hydrogen in tetrahydrofuran, Time= 0.8h, T= 50 °C , p= 3800.26Torr Patent; The Governing Council of the University of Toronto; MORRIS, Robert H.; LAGADITIS, Paraskevi Olympia; SONNENBERG, Jessica; (73 pag.); US2016/326202; (2016); (A1) English View in Reaxys

H HO

Rx-ID: 29526784 View in Reaxys 22/176

183/258

2018-07-03 17:29:03

Yield

Conditions & References With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, Butane-1,4-diol, N-[(1S,2S)-2-amino-1,2-diphenylethyl]-4-methylbenzenesulfonamide, potassium hydroxide, Time= 72h, T= 110 °C , optical yield given as percent ee Maytum, Hannah C.; Francos, Javier; Whatrup, David J.; Williams, Jonathan M. J.; Chemistry - An Asian Journal; vol. 5; nb. 3; (2010); p. 538 - 542 View in Reaxys With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, potassium tert-butylate, lithium chloride, t-butyl [(S)-1-((S)-2-hydroxypropylcarbamoyl)ethyl]carbamate in tetrahydrofuran, ethanol, Time= 3h, T= 40 °C , Inert atmosphere, Solvent, enantioselective reaction Slagbrand, Tove; Lundberg, Helena; Adolfsson, Hans; Chemistry - A European Journal; vol. 20; nb. 49; (2014); p. 16102 16106 View in Reaxys Reaction Steps: 2 1: [Ru(η3:η3-C10H16)Cl(η2-O,O-CH3CO2)] / aq. phosphate buffer / 2.5 h / 50 °C / pH 7 / Sealed tube; Inert atmosphere 2: NADPH; ketoreductase P2-D11 / aq. phosphate buffer; isopropyl alcohol / 24 h / 30 °C / pH 7 / Enzymatic reaction With [Ru(η3:η3-C10H16)Cl(η2-O,O-CH3CO2)], ketoreductase P2-D11, NADPH in aq. phosphate buffer, isopropyl alcohol Ríos-Lombardía, Nicolás; Vidal, Cristian; Liardo, Elisa; Morís, Francisco; García-Álvarez, Joaquín; González-Sabín, Javier; Angewandte Chemie - International Edition; vol. 55; nb. 30; (2016); p. 8691 - 8695; Angew. Chem.; vol. 128; nb. 30; (2016); p. 8833 - 8837,5 View in Reaxys

H OH

Rx-ID: 41933886 View in Reaxys 23/176 Yield 6.6 %

Conditions & References With tert.-butylhydroperoxide, potassium osmate, potassium hydroxide in methanol, decane, chloroform, Time= 168h, T= 0 °C , Enzymatic reaction, Sharpless Dihydroxylation, Catalytic behavior, Reagent/catalyst, Solvent, enantioselective reaction Leurs, Melanie; Spiekermann, Pia S.; Tiller, Joerg C.; ChemCatChem; vol. 8; nb. 3; (2016); p. 593 - 599 View in Reaxys

H HO

Rx-ID: 41933887 View in Reaxys 24/176 Yield

Conditions & References With tert.-butylhydroperoxide, potassium osmate, potassium hydroxide in methanol, decane, chloroform, Time= 168h, T= 4 °C , Enzymatic reaction, Sharpless Dihydroxylation, Catalytic behavior, Temperature, Overall yield = 8.4 percent; enantioselective reaction Leurs, Melanie; Spiekermann, Pia S.; Tiller, Joerg C.; ChemCatChem; vol. 8; nb. 3; (2016); p. 593 - 599 View in Reaxys

184/258

2018-07-03 17:29:03

H OH

Rx-ID: 2015382 View in Reaxys 25/176 Yield 48 %

Conditions & References 1 : [Example 1] At -30°C racemic alcohol (1a) 1.0 mmol wasdissolved in 5 ml of dichloromethane, the compound of formula 1 (wherein, R is I and n being 2) 1 molpercent as a catalyst, additionof 0.7 equivalents of silylating agent of formula (5) (in the formula, R4 is methyl) was stirred for 2 hours. The residue was purified by flash chromatography (acetone / hexane / triethylamine = 1: 5: 0.025) to give the chiral alcohol (2a, 48percent yield 98percent ee, (R)-form). With C46H34I4O6, 1,1,1,3,3,3-hexamethyl-disilazane in dichloromethane, Time= 2h, T= -30 °C , stereoselective reaction Patent; SUNGKYUNKWAN UNIVERSITY RESEARCH & BUSINESS FOUNDATION; SONG, CHUNG EUI; PARK, SANG YEON; LEE, JI WOONG; (43 pag.); KR2015/114167; (2015); (A) Korean View in Reaxys

48 %

1 : [Example 1] -30 ° C a racemic alcohol (1a) as a catalyst, 1.0 mmol was dissolved in 5 ml of dichloromethane in the compounds of the formula (wherein, R is I and n is 2; and pharmaceutically acceptable salts)and the addition of 1 molpercent Formula 5 the silylating agent (in the formula, R is methyl) to 0.7 equivalents was stirred for 2 hours was added. The residue was purified by flash chromatography (acetone / hexane / triethylamine= 1: 5: 0.025) to give the chiral alcohol; to give the (2a, 48percent yield 98percent ee,(R) -form). With C45H32I4O6, 1,1,1,3,3,3-hexamethyl-disilazane in dichloromethane, Time= 2h, T= -30 °C , stereoselective reaction Patent; RESEARCH & BUSINESS FOUNDATION SUNGKYUNKWAN UNIVERSITY; SONG, CHOON GEUI; PARK, SANG YEON; LEE, JI WOONG; (43 pag.); KR2015/114445; (2015); (A) Korean View in Reaxys

25 %

With air, cells of Geotrichum candidum IFO 5767 in water, Time= 24h, T= 30 °C Nakamura, Kaoru; Fujii, Mikio; Ida, Yoshiteru; Tetrahedron Asymmetry; vol. 12; nb. 22; (2001); p. 3147 - 3153 View in Reaxys

24 %

With Geotrichum candidum 34614 in various solvent(s), pH= 5.0 Homann, Michael J.; Vail, Robert B.; Previte, Edward; Tamarez, Maria; Morgan, Brian; Dodds, David R.; Zaks, Aleksey; Tetrahedron; vol. 60; nb. 3; (2004); p. 789 - 797 View in Reaxys With sodium hydroxide, tris(triphenylphosphine)ruthenium(II) chloride, (S)-(+)-2-(2-diphenylarsinophenyl)-4-(isopropyl)oxazoline in acetone, Time= 3h, T= 20 °C Tan, Duan-Ming; Chan, Kin Shing; Tetrahedron Letters; vol. 46; nb. 3; (2005); p. 503 - 505 View in Reaxys With (S)-Cl-PIQ Birman, Vladimir B.; Li, Ximin; Jiang, Hui; W. Uffman, Eric; Tetrahedron; vol. 62; nb. 2-3; (2006); p. 285 - 294 View in Reaxys Gutman, Arie L.; Brenner, Dov; Boltanski, Aviv; Tetrahedron: Asymmetry; vol. 4; nb. 5; (1993); p. 839 - 844 View in Reaxys Kanoh, Shigeyoshi; Hongoh, Yukihiko; Katoh, Shingo; Motoi, Masatoshi; Suda, Hiroshi; Journal of the Chemical Society, Chemical Communications; nb. 6; (1988); p. 405 - 406 View in Reaxys Reaction Steps: 2 1.1: triethylamine; chiral 4-diethylaminopyridine-based reagent / 9 h / -78 °C 1.2: methanol / 0.25 h / -78 - 20 °C 2.1: sodium hydroxide / methanol / 0.08 h / Heating With sodium hydroxide, chiral 4-diethylaminopyridine-based reagent, triethylamine in methanol

185/258

2018-07-03 17:29:03

Spivey, Alan C.; Arseniyadis, Stellios; Fekner, Tomasz; Maddaford, Adrian; Leese, David P.; Tetrahedron; vol. 62; nb. 2-3; (2006); p. 295 - 301 View in Reaxys Reaction Steps: 2 1: diisopropyl ether / 40 h / 30 °C / lipase QL 2: LiAlH4 / diethyl ether / 6 h / Heating With lithium aluminium tetrahydride in diethyl ether, di-isopropyl ether Naemura, Koichiro; Murata, Masaki; Tanaka, Rie; Yano, Masashi; Hirose, Keiji; Tobe, Yoshito; Tetrahedron Asymmetry; vol. 7; nb. 11; (1996); p. 3285 - 3294 View in Reaxys Reaction Steps: 2 2: 1 M ethanol. NaOH / 4 h / 25 °C With sodium hydroxide Bianchi, Daniele; Cesti, Pietro; Battistel, Ezio; Journal of Organic Chemistry; vol. 53; nb. 23; (1988); p. 5531 - 5534 View in Reaxys Reaction Steps: 2 1: 34 percent / benzene / 20 h / 21 °C / lipase Amano P/Celite 577 2: 1 M ethanol. NaOH / 4 h / 25 °C With sodium hydroxide in benzene Bianchi, Daniele; Cesti, Pietro; Battistel, Ezio; Journal of Organic Chemistry; vol. 53; nb. 23; (1988); p. 5531 - 5534 View in Reaxys Reaction Steps: 2 1: 61 percent / TosOH, molecular sieve 4 Angstroem / diethyl ether / 2 h / Ambient temperature 2: 83 percent / p-toluenesulfonic acid / methanol / 3 h With 4 A molecular sieve, toluene-4-sulfonic acid in methanol, diethyl ether Noe, Christian R.; Chemische Berichte; vol. 115; nb. 4; (1982); p. 1591 - 1606 View in Reaxys Reaction Steps: 2 1: immobilized CALB lipase / 32 h / 30 °C / Enzymatic reaction 2: immobilized CALB lipase; ammonia / di-isopropyl ether / 13 h / 35 °C / Enzymatic reaction With immobilized CALB lipase, ammonia in di-isopropyl ether Wang, Bo; Jiang, Ling; Wang, Jue; Ma, Jingbo; Liu, Min; Yu, Hongwei; Tetrahedron Asymmetry; vol. 22; nb. 9; (2011); p. 980 - 985 View in Reaxys Reaction Steps: 2 1: methanol / 80 °C 2: methanol / 72 h / 40 °C in methanol Lin, Lang; Yu, Rongmin; Wu, Xiao-Yuan; Yang, Wen-Bin; Zhang, Jian; Guo, Xiang-Guang; Lin, Zu-Jin; Lu, CanZhong; Inorganic Chemistry; vol. 53; nb. 10; (2014); p. 4794 - 4796 View in Reaxys 85 %Chromat.

186/258

2018-07-03 17:29:03

Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys

H (v2)

Rx-ID: 2681725 View in Reaxys 26/176 Yield 88 %

Conditions & References With hydrogenchloride, (-)-DAIB in toluene, T= 0 °C Kitamura, M.; Okada, S.; Suga, S.; Noyori, R.; Journal of the American Chemical Society; vol. 111; nb. 11; (1989); p. 4028 4036 View in Reaxys

76 %, 9 %

With tridentate lithium complex (6-Li salt) in toluene, Time= 7h, T= 0 °C , Yield given Corey, E. J.; Hannon, Francis J.; Tetrahedron Letters; vol. 28; nb. 44; (1987); p. 5233 - 5236 View in Reaxys

With (S)-(-)-2'-CH2OH-4'-Me[2]paracyclo[2](5',8')quinolinaphane in toluene, Time= 5h, T= 20 °C , Title compound not separated from byproducts Ruzziconi, Renzo; Piermatti, Oriana; Ricci, Giacomo; Vinci, Daniele; Synlett; nb. 5; (2002); p. 747 - 750 View in Reaxys With (+)-(1S,3S)-N,NI bis<benzyl>-1,3-diphenyl-1,3-propanediamine in toluene, Time= 20h, Ambient temperature, with the dilithium salt of the catalyst as well, Product distribution Pini, Dario; Mastantuono, Alberto; Uccello-Barretta, Gloria; Iuliano, Anna; Salvadori, Piero; Tetrahedron; vol. 49; nb. 42; (1993); p. 9613 - 9624 View in Reaxys

4 % Chromat.

With quinidine in toluene, Time= 0.25h, T= 100 °C , Yield given. Yields of byproduct given Muchow, G.; Vannoorenberghe, Y.; Buono, G.; Tetrahedron Letters; vol. 28; nb. 49; (1987); p. 6163 - 6166 View in Reaxys With (S)-N,N,N',N'-tetramethyl-[1,1'-binaphthalene]-2,2'-diamine in toluene, Ambient temperature, Yield given. Yields of byproduct given. Title compound not separated from byproducts Rosini, Carlo; Franzini, Livia; Iuliano, Anna; Pini, Dario; Salvadori, Piero; Tetrahedron: Asymmetry; vol. 2; nb. 5; (1991); p. 363 - 366 View in Reaxys With Octahydro-cyclopenta<b>pyrrol in hexane, T= 0 °C , various 2-azabicyclo<3.3.0>octanes, Product distribution Aurich, Hans Guenter; Soeberdt, Michael; Tetrahedron Letters; vol. 39; nb. 17; (1998); p. 2553 - 2554 View in Reaxys With C16H24N2O2 in hexane, Time= 12h, Ambient temperature, other reagents, Product distribution Aurich, Hans Guenter; Soeberdt, Michael; Harms, Klaus; Tetrahedron; vol. 55; nb. 5; (1999); p. 1249 - 1270 View in Reaxys

187/258

2018-07-03 17:29:03

With polymer-supported (1R,2S)-ephedrine in toluene, Time= 12h, T= 20 °C , Addition, Product distribution, Further Variations: Reagents Hodge, Philip; Sung, David W. L.; Stratford, Peter W.; Journal of the Chemical Society - Perkin Transactions 1; nb. 16; (1999); p. 2335 - 2342 View in Reaxys With (+)-camphor-1-ol-2-(2-morpholinoethyl) in toluene, Time= 17h, T= 20 °C , Addition, Product distribution, Further Variations: Reaction partners, Reagents, Solvents, Temperatures Knollmueller, Max; Ferencic, Mathias; Gaertner, Peter; Tetrahedron Asymmetry; vol. 10; nb. 20; (1999); p. 3969 - 3975 View in Reaxys With (P,P)-(+)-bis[5]helicene diol in toluene, Time= 24h, Addition, Title compound not separated from byproducts Dreher, Spencer D.; Katz, Thomas J.; Lam, Kin-Chung; Rheingold, Arnold L.; Journal of Organic Chemistry; vol. 65; nb. 3; (2000); p. 815 - 822 View in Reaxys With mesoporous aluminosilica supported (-)-ephedrine, T= 0 °C , Product distribution, Further Variations: Reagents Abramson; Lasperas; Brunel; Tetrahedron Asymmetry; vol. 13; nb. 4; (2002); p. 357 - 367 View in Reaxys With (R)-2-(N,N-dimethylamino)methyl-2'-hydroxy-1,1'-binaphthyl in toluene, Time= 24h, T= 20 °C , Product distribution, Further Variations: Reagents Ko, Dong-Hyun; Kim, Kyoung Hoon; Ha, Deok-Chan; Organic Letters; vol. 4; nb. 21; (2002); p. 3759 - 3762 View in Reaxys With (R,R,R)-2-benzyl-3-(Ph2(OH)methyl)-2-azabicyclo[3.3.0]octane in toluene, Time= 24h, T= 25 °C , Product distribution, Further Variations: Reagents Burguete, M. Isabel; Garcia-Verdugo, Eduardo; Vicent, Maria J.; Luis, Santiago V.; Pennemann, Helmut; Graf Von Keyserling, Nikolai; Martens, Jurgen; Organic Letters; vol. 4; nb. 22; (2002); p. 3947 - 3950 View in Reaxys With chiral pentacyclo-undecane cage annulated ligand in toluene, Time= 30h, T= 20 °C , Product distribution, Further Variations: Reagents Boyle, Grant A.; Govender, Thavendran; Kruger, Hendrik G.; Maguire, Glenn E.M.; Tetrahedron Asymmetry; vol. 15; nb. 17; (2004); p. 2661 - 2666 View in Reaxys With (R,R,R)-2-benzyl-3-(Ph2(OH)methyl)-2-azabicyclo[3.3.0]octane in toluene, Time= 24h, T= 25 °C , Product distribution, Further Variations: Catalysts Burguete, M. Isabel; Garcia-Verdugo, Eduardo; Vicent, Maria J.; Luis, Santiago V.; Pennemann, Helmut; Graf Von Keyserling, Nikolai; Martens, Jurgen; Organic Letters; vol. 4; nb. 22; (2002); p. 3947 - 3950 View in Reaxys With chiral bicyclo[3.2.1]octane-based alcohol in hexane, toluene, Time= 24h, T= 20 °C , Title compound not separated from byproducts Scarpi, Dina; Galbo, Fabrizio Lo; Guarna, Antonio; Tetrahedron Asymmetry; vol. 17; nb. 9; (2006); p. 1409 - 1414 View in Reaxys 22 %Chromat.

Stage 1: With (S,E)-2-(1-(1-phenylethylimino)ethyl)phenol in hexane, toluene, T= 0 °C , Inert atmosphere Stage 2: in hexane, toluene, T= 0 - 20 °C , Inert atmosphere, optical yield given as percent ee Jaworska, Magdalena; Welniak, Miroslaw; Zieciak, Justyna; Kozakiewicz, Anna; Wojtczakb, Andrzej; Arkivoc; vol. 2011; nb. 9; (2011); p. 189 - 204 View in Reaxys Stage 1: With Ni(II) complex from η-amino amide supported on Merrield resin with 1:1 stoichiometry in toluene, Time= 0.166667h, T= 0 °C , Green chemistry

188/258

2018-07-03 17:29:03

Stage 2: in toluene, Time= 36h, T= 0 °C , Inert atmosphere, Green chemistry, Kinetics, Catalytic behavior, Solvent, Temperature, Overall yield = 91 percent; enantioselective reaction Escorihuela, Jorge; Altava, Beln; Burguete, M. Isabel; Luis, Santiago V.; RSC Advances; vol. 5; nb. 19; (2015); p. 14653 14662 View in Reaxys Stage 1: With polystyrene supported nickel(II) complexes derived from η-amino amides in toluene, Time= 0.166667h, T= 0 °C , Green chemistry Stage 2: in toluene, Time= 36h, T= 0 °C , Inert atmosphere, Green chemistry, Kinetics, Solvent, Temperature, Overall yield = 98 percent; enantioselective reaction Escorihuela, Jorge; Altava, Beln; Burguete, M. Isabel; Luis, Santiago V.; RSC Advances; vol. 5; nb. 19; (2015); p. 14653 14662 View in Reaxys

Cl Cl

Rx-ID: 3691542 View in Reaxys 27/176 Yield 33 %

Conditions & References With potassium fluoride, dihydrogen peroxide, potassium hydrogencarbonate in tetrahydrofuran, methanol, water, Time= 21h, T= 20 °C , Inert atmosphere, Tamao-Kumada Oxidation Nagata, Yuuya; Nishikawa, Tsuyoshi; Suginome, Michinori; Journal of the American Chemical Society; vol. 137; nb. 12; (2015); p. 4070 - 4073 View in Reaxys With potassium fluoride, dihydrogen peroxide, potassium hydrogencarbonate in tetrahydrofuran, methanol, Time= 10h, Ambient temperature, Yield given Uozumi, Yasuhiro; Kitayama, Kenji; Hayashi, Tamio; Tetrahedron: Asymmetry; vol. 4; nb. 12; (1993); p. 2419 - 2422 View in Reaxys With potassium fluoride, dihydrogen peroxide, potassium hydrogencarbonate in tetrahydrofuran, methanol Guo, Xun-Xiang; Xie, Jian-Hua; Hou, Guo-Hua; Shi, Wen-Jian; Wang, Li-Xin; Zhou, Qi-Lin; Tetrahedron Asymmetry; vol. 15; nb. 14; (2004); p. 2231 - 2234 View in Reaxys With potassium fluoride, dihydrogen peroxide, potassium hydrogencarbonate in tetrahydrofuran, methanol, Time= 16h, T= 20 °C , Tamao oxidation Jensen, Jakob F.; Svendsen, Bo Y.; La Cour, Thomas V.; Pedersen, Henriette L.; Johannsen, Mogens; Journal of the American Chemical Society; vol. 124; nb. 17; (2002); p. 4558 - 4559 View in Reaxys Determination of enantiomeric excess of the hydrosilylation product: To a mixture of the hydrosilylation product (191.7 mg, 0.8 mmol), KF (278.9 mg, 4.8 mmol), and KHCO3 (720.8 mg, 7.2 mmol) in THF (4 mL) and MeOH (4 mL) was added hydrogen peroxide (30 wt.percent, 9.6 mmol) at room temperature. The mixture was stirred at room temperature for 17 h. To the mixture was added sat. Na2S2O3 aq. Organic materials were extracted with ether (50 mL), washed with water (50 mL) and brine (50 mL), and dried over Na2SO4. After evaporation of the solvent, the residue was subjected to bulb-to-bulb distillation giving enantioenriched 1-phenylethanol. The enantiomeric excess of the product was determined to be 97percent by HPLC with CHIRALCEL® OD-H (Eluent: Hexane/2-PrOH = 97/3, Flow rate: 0.6 mL/min, Retention time: tR of (R)-isomer = 18.4 min, tR of (S)-isomer = 20.5 min). With potassium fluoride, dihydrogen peroxide, potassium hydrogencarbonate in tetrahydrofuran, methanol, Time= 17h, T= 20 °C , Inert atmosphere Nagata, Yuuya; Ke, Yuan-Zhen; Suginome, Michinori; Chemistry Letters; vol. 44; nb. 1; (2015); p. 53 - 55

189/258

2018-07-03 17:29:03

View in Reaxys

H (v2)

H HO

O OH

Rx-ID: 5206912 View in Reaxys 28/176 Yield 98 %, 2 %

Conditions & References With polymer-supported (1R,2S)-ephedrine in toluene, Time= 12h, T= 20 °C , Addition Hodge, Philip; Sung, David W. L.; Stratford, Peter W.; Journal of the Chemical Society - Perkin Transactions 1; nb. 16; (1999); p. 2335 - 2342 View in Reaxys

98 %

Stage 1: With polystyrene supported nickel(II) complexes derived from η-amino amides in toluene, Time= 0.166667h, T= -25 °C , Green chemistry Stage 2: in toluene, Time= 36h, T= -25 °C , Inert atmosphere, Green chemistry, Kinetics, Solvent, Temperature, enantioselective reaction Escorihuela, Jorge; Altava, Beln; Burguete, M. Isabel; Luis, Santiago V.; RSC Advances; vol. 5; nb. 19; (2015); p. 14653 14662 View in Reaxys

92 %

4.6. General procedure for the addition of ZnR2 to aldehydes General procedure: The Ni complex (0.1 equiv) was dissolved in anhydrous toluene(10 mL) in a Schlenk tube. The solution was stirred and cooled at0 C for 30 min, and then a solution of Et2Zn (1.1 M in toluene) orMe2Zn (1.0 M in toluene) (12 equiv) was added dropwise via a syringeunder N2 atmosphere. After stirring the mixture for 30 min atroom temperature, a solution of aldehyde (10 equiv) in dry toluenewas added dropwise via a syringe. The mixture was stirred at roomtemperature for 8 h, quenched with 1 M HCl aqueous (5 mL), andthe product was extracted into Et2O (310 mL). The combinedextracts were washed with KHCO3, dried with anhydrous MgSO4,and evaporated under vacuum. Purification by column chromatography(silica gel, 9:1 hexane/AcOEt as eluent) gave the pure alcoholas a colorless oil. All reactions were carried out using0.1e0.2 mL of aldehyde. The conversion and the selectivity of thereaction were determined by NMR spectroscopy, and the enantioselectivitywas determined by HPLC or GC on a chiral stationaryphase Stage 1: With C32H34N4NiO2 in toluene, Time= 0.5h, T= 0 - 20 °C , Inert atmosphere, Schlenk technique Stage 2: in toluene, Time= 14h, T= 20 °C , Schlenk technique, Inert atmosphere, Solvent, enantioselective reaction Escorihuela, Jorge; Altava, Belen; Burguete, M. Isabel; Luis, Santiago V.; Tetrahedron; vol. 69; nb. 2; (2013); p. 551 - 558 View in Reaxys With (1R,2S)-(+)-1-cyclohexyl-2-phenyl-2-(N-morpholino)ethanol in hexane, toluene, Time= 3h, T= 20 °C , Title compound not separated from byproducts. Nugent, William A.; Organic Letters; vol. 4; nb. 13; (2002); p. 2133 - 2136 View in Reaxys

H OH

Rx-ID: 39736496 View in Reaxys 29/176 Yield

Conditions & References Reaction Steps: 2 1: bis(η3-allyl-μ-chloropalladium(II)); trichlorosilane / chloroform / 24 h / 20 °C / Inert atmosphere 2: potassium hydrogencarbonate; dihydrogen peroxide; potassium fluoride / tetrahydrofuran; water; methanol / 21 h / 20 °C / Inert atmosphere With potassium fluoride, bis(η3-allyl-μ-chloropalladium(II)), trichlorosilane, dihydrogen peroxide, potassium hydrogencarbonate in tetrahydrofuran, methanol, chloroform, water, 2: |Tamao-Kumada Oxidation Nagata, Yuuya; Nishikawa, Tsuyoshi; Suginome, Michinori; Journal of the American Chemical Society; vol. 137; nb. 12; (2015); p. 4070 - 4073

190/258

2018-07-03 17:29:03

View in Reaxys Reaction Steps: 2 1: bis(η3-allyl-μ-chloropalladium(II)); trichlorosilane / chloroform; 1,1,2,2-tetrachloroethane / 24 h / 20 °C / Inert atmosphere 2: potassium hydrogencarbonate; dihydrogen peroxide; potassium fluoride / tetrahydrofuran; water; methanol / 21 h / 20 °C / Inert atmosphere With potassium fluoride, bis(η3-allyl-μ-chloropalladium(II)), trichlorosilane, dihydrogen peroxide, potassium hydrogencarbonate in tetrahydrofuran, methanol, chloroform, water, 1,1,2,2-tetrachloroethane, 2: |Tamao-Kumada Oxidation Nagata, Yuuya; Nishikawa, Tsuyoshi; Suginome, Michinori; Journal of the American Chemical Society; vol. 137; nb. 12; (2015); p. 4070 - 4073 View in Reaxys

O OH

Rx-ID: 41583795 View in Reaxys 30/176 Yield

Conditions & References With esterase from archaeon Sulfolobus tokodaii strain 7 in aq. buffer, Time= 2h, T= 30 °C , pH= 8, Resolution of racemate, Enzymatic reaction Wada, Reina; Ozaki, Masanaru; Kumon, Takashi; Ohta, Hiromichi; Miyamoto, Kenji; Biocatalysis and Biotransformation; vol. 33; nb. 3; (2015); p. 188 - 190 View in Reaxys

O OH

Rx-ID: 41657186 View in Reaxys 31/176 Yield

Conditions & References

97 %

With benzyl[(1R,2R)-2-[(diphenylphosphoroso)amino]-1,2-diphenylethyl]amine, diethylzinc in toluene, Time= 12h, T= -20 °C , Temperature, enantioselective reaction Huang, Huayin; Zong, Hua; Bian, Guangling; Song, Ling; Journal of Organic Chemistry; vol. 80; nb. 24; (2015); p. 12614 12619 View in Reaxys O

H (v2)

OH Cl

Rx-ID: 41657187 View in Reaxys 32/176 Yield

Conditions & References Stage 1: With benzyl[(1R,2R)-2-[(diphenylphosphoroso)amino]-1,2-diphenylethyl]amine in toluene, Time= 0.5h, T= 0 °C , Inert atmosphere, Schlenk technique Stage 2: in toluene, Time= 48h, T= -20 °C , Inert atmosphere, Schlenk technique, enantioselective reaction Huang, Huayin; Zong, Hua; Bian, Guangling; Song, Ling; Journal of Organic Chemistry; vol. 80; nb. 24; (2015); p. 12614 12619

191/258

2018-07-03 17:29:03

View in Reaxys

O H

(v2)

F F F

HO F

F F

HO F

F F F F

F F

Rx-ID: 41657188 View in Reaxys 33/176 Yield

F (v2)

F H

F OH

Rx-ID: 41657195 View in Reaxys 34/176 Yield

Conditions & References

99 %

Stage 1: With benzyl[(1R,2R)-2-[(diphenylphosphoroso)amino]-1,2-diphenylethyl]amine in toluene, Time= 0.5h, T= 0 °C , Inert atmosphere, Schlenk technique Stage 2: in toluene, Time= 48h, T= -20 °C , Inert atmosphere, Schlenk technique, enantioselective reaction Huang, Huayin; Zong, Hua; Bian, Guangling; Song, Ling; Journal of Organic Chemistry; vol. 80; nb. 24; (2015); p. 12614 12619 View in Reaxys O

H (v2)

Rx-ID: 41657196 View in Reaxys 35/176 Yield 89 %

192/258

2018-07-03 17:29:03

Mg Br

H O

Rx-ID: 2681707 View in Reaxys 36/176 Yield

Conditions & References With (R,R)-TADDOL in tetrahydrofuran, T= -105 °C , Title compound not separated from byproducts Weber, Beat; Seebach, Dieter; Tetrahedron; vol. 50; nb. 20; (1994); p. 6117 - 6128 View in Reaxys With (5aS,10aS)-(-)-Octahydro-5H,10H-dipyrrolo<1,2-a:1',2'-d>pyrazin in tetrahydrofuran, toluene, Time= 5h, T= -100 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Zadel, Guido; Breitmaier, Eberhard; Chemische Berichte; vol. 127; nb. 7; (1994); p. 1323 - 1326 View in Reaxys With tetraphenyl-TADDOL-derivative 1a, 1. ether, -70 deg C to r.t.; 2. -100 deg C, 9 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Weber, Beat; Seebach, Dieter; Angewandte Chemie; vol. 104; nb. 1; (1992); p. 96 - 97 View in Reaxys With (R,R)-TADDOL in diethyl ether, T= -105 °C , Title compound not separated from byproducts Weber, Beat; Seebach, Dieter; Tetrahedron; vol. 50; nb. 20; (1994); p. 6117 - 6128 View in Reaxys With triethylamine, (5aS,10aS)-(-)-Octahydro-5H,10H-dipyrrolo<1,2-a:1',2'-d>pyrazin in tetrahydrofuran, toluene, Time= 5h, T= -100 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Zadel, Guido; Breitmaier, Eberhard; Chemische Berichte; vol. 127; nb. 7; (1994); p. 1323 - 1326 View in Reaxys With 1,4-dioxane, titanium(IV) isopropylate, (4R,5R)-2,2-dimethyl-η,η,η',η'-tetra(naphth-2-yl)-1,3-dioxolan-4,5-dimethoxydiisopropoxy titanate, zinc(II) chloride, 1a.) Et2O, r.t., 2 h, 1b.) 45 min, 2a.) -78 deg C, 1 h, 2b) -30 deg C, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Bussche-Huennefeld, Joanna Linda v.; Seebach, Dieter; Tetrahedron; vol. 48; nb. 27; (1992); p. 5719 - 5730 View in Reaxys With chiral podand crown ether in toluene, Time= 24h, Product distribution, Further Variations: Catalysts Luk'yanenko; Lobach; Leus; Russian Journal of Organic Chemistry; vol. 40; nb. 2; (2004); p. 273 - 277 View in Reaxys Title compound not separated from byproducts. Chen; Costa; Walsh; Journal of the American Chemical Society; vol. 123; nb. 22; (2001); p. 5378 - 5379 View in Reaxys Stage 1: With titanium(IV) isopropylate, Bis<2-(N,N-dimethylamino)aethyl>aether, (S)-[1,1']-binaphthalenyl-2,2'-diol in tetrahydrofuran, tert-butyl methyl ether, T= 20 °C , Inert atmosphere, Cooling with ice Stage 2: in tetrahydrofuran, tert-butyl methyl ether, T= 20 °C , Inert atmosphere, Cooling with ice, optical yield given as percent ee, enantioselective reaction Da, Chao-Shan; Wang, Jun-Rul; Yin, Xiao-Gang; Fan, Xin-Yuan; Liu, Yi; Yu, Sheng-Li; Organic Letters; vol. 11; nb. 24; (2009); p. 5578 - 5581 View in Reaxys

193/258

2018-07-03 17:29:03

Stage 1: With titanium(IV) isopropylate, Bis<2-(N,N-dimethylamino)aethyl>aether, (S)-[1,1']-binaphthalenyl-2,2'-diol in tetrahydrofuran, tert-butyl methyl ether, T= 20 °C , Inert atmosphere, Cooling with ice-salt bath Stage 2: in tetrahydrofuran, tert-butyl methyl ether, T= 20 °C , Inert atmosphere, Cooling with ice-salt bath, optical yield given as percent ee, enantioselective reaction Liu, Yi; Da, Chao-Shan; Yu, Sheng-Li; Yin, Xiao-Gang; Wang, Jun-Rui; Fan, Xin-Yuan; Li, Wei-Ping; Wang, Rui; Journal of Organic Chemistry; vol. 75; nb. 20; (2010); p. 6869 - 6878 View in Reaxys Stage 1: With zinc diacetate in tert-butyl methyl ether, Time= 1h, T= 0 - 20 °C Stage 2: With 2Br(1-)*C31H28O4 (2-)*2Mg(2+) in tert-butyl methyl ether, Time= 8h, T= 20 °C , optical yield given as percent ee, enantioselective reaction Jagtap; Joshi; Tetrahedron Letters; vol. 52; nb. 48; (2011); p. 6501 - 6503 View in Reaxys 6. General procedure for the asymmetric addition of EtMgBr with benzaldehyde General procedure: 0.5 mmol Poly-(S)-EFPO (4a) and EtMgBr (1M in THF; 2 mL, 2 mmol) was added to a solution of titanium tetraisopropoxide (1.5 mmol) in dry THF (16 mL) at0oC in an argon atmosphere. After stirring the reaction for 30 min at this temperature,it was slowly added (over a period of 2 h by using a syringe pump) to a solution of ZnCl2 (1 mmol) and benzaldehyde (0.106 g, 1.0 mmol) in THF (4 mL) at -15oC in an argon atmosphere and stirred for a further 24 h. The reaction mixture was then quenched by the addition of aqueous 1N HCl and extracted three times with Et2O.The organic layers were washed successively with aqueous 5percent NaHCO3 and brine, dried (MgSO4), and concentrated in vacuo. The residue was added into 25 mL of methanol. The mixture was irradiated with ultrasound (53 W, 40 kHz) for 30 min and,then, filtrated. The filtrate was concentrated under reduced pressure and the residue was chromatographed on silica gel to obtain the addition product. The ee of the product was measured with chiral HPLC. Stage 1: With titanium(IV) isopropylate in tetrahydrofuran, Time= 0.5h, T= 0 °C , Inert atmosphere Stage 2: With zinc(II) chloride in tetrahydrofuran, Time= 24h, T= -15 °C , Inert atmosphere, Reagent/catalyst, Overall yield = 75 percent; enantioselective reaction Zhang, Anlin; Yang, Nianfa; Yang, Liwen; Peng, Dan; Chemistry Letters; vol. 43; nb. 4; (2014); p. 462 - 464 View in Reaxys

H HO

Rx-ID: 11162403 View in Reaxys 37/176 Yield 81 %

Conditions & References With novozyme 435 in toluene, Time= 4h, T= 60 °C Bachu, Prabhakar; Gibson, Jennifer S.; Sperry, Jonathan; Brimble, Margaret A.; Tetrahedron Asymmetry; vol. 18; nb. 13; (2007); p. 1618 - 1624 View in Reaxys General procedure for dynamic kinetic resolution of rac-alcohols General procedure: To a 25 mL Schlenk tube containing 5 mL toluene, Ru or Ir complex (0.01 mmol, 2.0 molpercent) and potassium tert-butoxide (0.04mmol, 5.0molpercent) were added and stirred for 10min. Sodium carbonate (0.5mmol), alcohol (0.5mmol), acylating agents (1.5mmol) and Novozym-435 (10mg) were then added. The solvent was then stirred for 24hat 60°C or 70°C. After evaporation to dryness, the mixture was loaded to a 10×3cm silica column. Elution with petroleum ether removed any alcohol. The product was eluted with 3:50 ethyl acetate/petroleum ether, and the solvent removed to give an oily mixture. The yield was directly determined by 1H NMR. Enantiomeric excesses were determined by specific rotation, HPLC or GC. With [(η6-p-cymene)RuCl2(pyridine)], potassium tert-butylate, sodium carbonate in toluene, Time= 48h, T= 70 °C , Inert atmosphere, Schlenk technique, Enzymatic reaction, Overall yield = 63 percentSpectr.; Optical yield = 73 percent ee; enantioselective reaction

194/258

2018-07-03 17:29:03

Cao, Hui; Cai, Li-Hua; Wang, Chen-Xi; Zhu, Xiao-Han; Li, Zhi-Ming; Hou, Xiu-Feng; Journal of Organometallic Chemistry; vol. 775; (2014); p. 60 - 66 View in Reaxys

H O

Rx-ID: 23827433 View in Reaxys 38/176 Yield

Conditions & References Reaction Steps: 2 1: tetrahydrofuran / 0 - 20 °C / Inert atmosphere 2: [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; t-butyl [(S)-1-((S)-2-hydroxypropylcarbamoyl)ethyl]carbamate; lithium chloride; potassium tert-butylate / tetrahydrofuran; ethanol / 3 h / 40 °C / Inert atmosphere With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2, potassium tert-butylate, lithium chloride, t-butyl [(S)-1-((S)-2-hydroxypropylcarbamoyl)ethyl]carbamate in tetrahydrofuran, ethanol Slagbrand, Tove; Lundberg, Helena; Adolfsson, Hans; Chemistry - A European Journal; vol. 20; nb. 49; (2014); p. 16102 16106 View in Reaxys

O Si O

H HO

Rx-ID: 37888405 View in Reaxys 39/176 Yield

Conditions & References With hydrogenchloride in water, Time= 1h, T= 0 °C , Inert atmosphere Lowicki, Daniel; Bezlada, Agata; Mlynarski, Jacek; Advanced Synthesis and Catalysis; vol. 356; nb. 2-3; (2014); p. 591 - 595 View in Reaxys

H O

Rx-ID: 37992506 View in Reaxys 40/176 Yield

Conditions & References With C31H22N2, N-ethyl-N,N-diisopropylamine in chloroform, Time= 8h, T= 0 °C , Resolution of racemate, Reagent/catalyst, Solvent, Overall yield = 56.2 percentChromat.; enantioselective reaction Wang, Zheng; Ye, Jinjin; Wu, Rui; Liu, Yang-Zi; Fossey, John S.; Cheng, Jiagao; Deng, Wei-Ping; Catalysis Science and Technology; vol. 4; nb. 7; (2014); p. 1909 - 1913 View in Reaxys

195/258

2018-07-03 17:29:03

O (v2)

–O

O–

N (v2)

Cu +

HN NH N

O (v2)

–

O–

N (v2)

H HO

N Cu +

Rx-ID: 38066953 View in Reaxys 41/176 Yield

Conditions & References in methanol, Time= 72h, T= 40 °C Lin, Lang; Yu, Rongmin; Wu, Xiao-Yuan; Yang, Wen-Bin; Zhang, Jian; Guo, Xiang-Guang; Lin, Zu-Jin; Lu, CanZhong; Inorganic Chemistry; vol. 53; nb. 10; (2014); p. 4794 - 4796 View in Reaxys H N

N HO

O (v2)

–O

O–

N (v2)

H HO

N 2

Cu +

Rx-ID: 38066962 View in Reaxys 42/176 Yield

Conditions & References Reaction Steps: 2 1: water / 72 h / 100 °C / Sealed tube 2: methanol / 72 h / 40 °C in methanol, water Lin, Lang; Yu, Rongmin; Wu, Xiao-Yuan; Yang, Wen-Bin; Zhang, Jian; Guo, Xiang-Guang; Lin, Zu-Jin; Lu, CanZhong; Inorganic Chemistry; vol. 53; nb. 10; (2014); p. 4794 - 4796 View in Reaxys

196/258

2018-07-03 17:29:03

H N N O

N H

O H N

O (v2)

–

O–

N (v2)

N Cu +

Rx-ID: 38066975 View in Reaxys 43/176 Yield

O (v2)

–O

O–

N (v2)

Cu +

HN NH N

O (v2)

–O

O– HN

H HO

N (v2)

N 2

Cu +

Rx-ID: 38066986 View in Reaxys 44/176 Yield

197/258

2018-07-03 17:29:03

H O

Rx-ID: 39087136 View in Reaxys 45/176 Yield

Cl H OH

OH O

Cl HO

Rx-ID: 39115174 View in Reaxys 46/176 Yield 21 %Chromat.

Conditions & References Screening procedure General procedure: Erlenmeyer flasks (300 ml), each containing 100 ml of the mediumconsisting of 3 g glucose and 1 g aminobac dissolved in water,were inoculated with a suspension of microorganisms and then incubated for 3–7 days at 25 C on a rotary shaker (190 rpm). After full growth of the culture 20 mg of a substrate dissolved in 1 ml of acetone was added. After 1, 3, 6, 9, 12 h and 1, 3, 6, 9 days of incubation under the above conditions, portions of 5 ml of the transformation mixture were taken out and extracted with CHCl3(3*10 ml). The extracts were dried over MgSO4, concentrated in vacuo, and analyzed by GC. All the experiments were repeatedthree times. With yeast culture of Aphanocladium album KCh 417 in acetone, Time= 144h, T= 25 °C , Microbiological reaction, enantioselective reaction Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys

33 %Chromat.

198/258

2018-07-03 17:29:03

With yeast culture of Saccharomyces cerevisiae KCh 464 in acetone, Time= 144h, T= 25 °C , Microbiological reaction, enantioselective reaction Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys 33 %Chromat.

OH O

Cl H HO

Rx-ID: 39115175 View in Reaxys 47/176 Yield

Conditions & References

7 %Chromat., 21 %Chromat.

199/258

2018-07-03 17:29:03

OH O

H OH

Rx-ID: 39115176 View in Reaxys 48/176 Yield

Conditions & References

29 %Chromat., 33 %Chromat.

28 %Chromat., 57 %Chromat.

Cl H HO

Rx-ID: 39115178 View in Reaxys 49/176 Yield

Conditions & References Reaction Steps: 2 1: yeast culture of Candida viswanathii KCh 120 / acetone / 144 h / 25 °C / Microbiological reaction 2: yeast culture of Rhodotorula rubra KCh 4 / acetone / 216 h / 25 °C / Microbiological reaction With yeast culture of Candida viswanathii KCh 120, yeast culture of Rhodotorula rubra KCh 4 in acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 2 1: yeast culture of Candida viswanathii KCh 120 / acetone / 6 h / 25 °C / Microbiological reaction 2: yeast culture of Rhodotorula rubra KCh 4 / acetone / 216 h / 25 °C / Microbiological reaction With yeast culture of Candida viswanathii KCh 120, yeast culture of Rhodotorula rubra KCh 4 in acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys

200/258

2018-07-03 17:29:03

Reaction Steps: 2 1: yeast culture of Rhodotorula glutinis KCh 242 / acetone / 6 h / 25 °C / Microbiological reaction 2: yeast culture of Rhodotorula rubra KCh 4 / acetone / 216 h / 25 °C / Microbiological reaction With yeast culture of Rhodotorula glutinis KCh 242, yeast culture of Rhodotorula rubra KCh 4 in acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 2 1: yeast culture of Rhodotorula rubra KCh 4 / acetone / 24 h / 25 °C / Microbiological reaction 2: yeast culture of Rhodotorula rubra KCh 4 / acetone / 216 h / 25 °C / Microbiological reaction With yeast culture of Rhodotorula rubra KCh 4 in acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 2 1: yeast culture of Rhodotorula rubra KCh 82 / acetone / 24 h / 25 °C / Microbiological reaction 2: yeast culture of Rhodotorula rubra KCh 4 / acetone / 216 h / 25 °C / Microbiological reaction With yeast culture of Rhodotorula rubra KCh 82, yeast culture of Rhodotorula rubra KCh 4 in acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 2 1: yeast culture of Rhodotorula rubra KCh 82 / acetone / 6 h / 25 °C / Microbiological reaction 2: yeast culture of Rhodotorula rubra KCh 4 / acetone / 216 h / 25 °C / Microbiological reaction With yeast culture of Rhodotorula rubra KCh 82, yeast culture of Rhodotorula rubra KCh 4 in acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 2 1: yeast culture of Saccharomyces brasiliensis KCh 905 / acetone / 24 h / 25 °C / Microbiological reaction 2: yeast culture of Rhodotorula rubra KCh 4 / acetone / 216 h / 25 °C / Microbiological reaction With yeast culture of Saccharomyces brasiliensis KCh 905, yeast culture of Rhodotorula rubra KCh 4 in acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 2 1: yeast culture of Saccharomyces cerevisiae KCh 464 / acetone / 144 h / 25 °C / Microbiological reaction 2: yeast culture of Rhodotorula rubra KCh 4 / acetone / 216 h / 25 °C / Microbiological reaction With yeast culture of Saccharomyces cerevisiae KCh 464, yeast culture of Rhodotorula rubra KCh 4 in acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 2 1: yeast culture of Yarrowia lipolytica ATCC 32-338 A / acetone / 72 h / 25 °C / Microbiological reaction 2: yeast culture of Rhodotorula rubra KCh 4 / acetone / 216 h / 25 °C / Microbiological reaction With yeast culture of Yarrowia lipolytica ATCC 32-338 A, yeast culture of Rhodotorula rubra KCh 4 in acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 3 1: yeast culture of Candida viswanathii KCh 120 / acetone / 144 h / 25 °C / Microbiological reaction 2: sodium tetrahydroborate / methanol 3: yeast culture of Yarrowia lipolytica KCh 71 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys

201/258

2018-07-03 17:29:03

Reaction Steps: 3 1: yeast culture of Candida viswanathii KCh 120 / acetone / 6 h / 25 °C / Microbiological reaction 2: sodium tetrahydroborate / methanol 3: yeast culture of Yarrowia lipolytica KCh 71 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 3 1: yeast culture of Rhodotorula glutinis KCh 242 / acetone / 6 h / 25 °C / Microbiological reaction 2: sodium tetrahydroborate / methanol 3: yeast culture of Yarrowia lipolytica KCh 71 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 3 1: yeast culture of Rhodotorula rubra KCh 4 / acetone / 24 h / 25 °C / Microbiological reaction 2: sodium tetrahydroborate / methanol 3: yeast culture of Yarrowia lipolytica KCh 71 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 3 1: yeast culture of Rhodotorula rubra KCh 82 / acetone / 24 h / 25 °C / Microbiological reaction 2: sodium tetrahydroborate / methanol 3: yeast culture of Yarrowia lipolytica KCh 71 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 3 1: yeast culture of Rhodotorula rubra KCh 82 / acetone / 6 h / 25 °C / Microbiological reaction 2: sodium tetrahydroborate / methanol 3: yeast culture of Yarrowia lipolytica KCh 71 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 3 1: yeast culture of Saccharomyces brasiliensis KCh 905 / acetone / 24 h / 25 °C / Microbiological reaction 2: sodium tetrahydroborate / methanol 3: yeast culture of Yarrowia lipolytica KCh 71 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 3 1: yeast culture of Saccharomyces cerevisiae KCh 464 / acetone / 144 h / 25 °C / Microbiological reaction 2: sodium tetrahydroborate / methanol 3: yeast culture of Yarrowia lipolytica KCh 71 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 3 1: yeast culture of Yarrowia lipolytica ATCC 32-338 A / acetone / 72 h / 25 °C / Microbiological reaction

202/258

2018-07-03 17:29:03

2: sodium tetrahydroborate / methanol 3: yeast culture of Yarrowia lipolytica KCh 71 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys

O O

Cl H HO

Rx-ID: 39115179 View in Reaxys 50/176 Yield 32 %Chromat.

Conditions & References Screening procedure General procedure: Erlenmeyer flasks (300 ml), each containing 100 ml of the mediumconsisting of 3 g glucose and 1 g aminobac dissolved in water,were inoculated with a suspension of microorganisms and then incubated for 3–7 days at 25 C on a rotary shaker (190 rpm). After full growth of the culture 20 mg of a substrate dissolved in 1 ml of acetone was added. After 1, 3, 6, 9, 12 h and 1, 3, 6, 9 days of incubation under the above conditions, portions of 5 ml of the transformation mixture were taken out and extracted with CHCl3(3*10 ml). The extracts were dried over MgSO4, concentrated in vacuo, and analyzed by GC. All the experiments were repeatedthree times. With yeast culture of Rhodotorula rubra KCh 4 in acetone, Time= 216h, T= 25 °C , Microbiological reaction, enantioselective reaction Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys

8 %Chromat.

58 %Chromat.

203/258

2018-07-03 17:29:03

Cl H OH

Rx-ID: 39115181 View in Reaxys 51/176 Yield

Conditions & References Reaction Steps: 2 1: yeast culture of Candida viswanathii KCh 120 / acetone / 144 h / 25 °C / Microbiological reaction 2: yeast culture of Candida viswanathii KCh 120 / acetone / 216 h / 25 °C / Microbiological reaction With yeast culture of Candida viswanathii KCh 120 in acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 2 1: yeast culture of Candida viswanathii KCh 120 / acetone / 6 h / 25 °C / Microbiological reaction 2: yeast culture of Candida viswanathii KCh 120 / acetone / 216 h / 25 °C / Microbiological reaction With yeast culture of Candida viswanathii KCh 120 in acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 2 1: yeast culture of Rhodotorula glutinis KCh 242 / acetone / 6 h / 25 °C / Microbiological reaction 2: yeast culture of Candida viswanathii KCh 120 / acetone / 216 h / 25 °C / Microbiological reaction With yeast culture of Rhodotorula glutinis KCh 242, yeast culture of Candida viswanathii KCh 120 in acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 2 1: yeast culture of Rhodotorula rubra KCh 4 / acetone / 24 h / 25 °C / Microbiological reaction 2: yeast culture of Candida viswanathii KCh 120 / acetone / 216 h / 25 °C / Microbiological reaction With yeast culture of Rhodotorula rubra KCh 4, yeast culture of Candida viswanathii KCh 120 in acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 2 1: yeast culture of Rhodotorula rubra KCh 82 / acetone / 24 h / 25 °C / Microbiological reaction 2: yeast culture of Candida viswanathii KCh 120 / acetone / 216 h / 25 °C / Microbiological reaction With yeast culture of Rhodotorula rubra KCh 82, yeast culture of Candida viswanathii KCh 120 in acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 2 1: yeast culture of Rhodotorula rubra KCh 82 / acetone / 6 h / 25 °C / Microbiological reaction 2: yeast culture of Candida viswanathii KCh 120 / acetone / 216 h / 25 °C / Microbiological reaction With yeast culture of Rhodotorula rubra KCh 82, yeast culture of Candida viswanathii KCh 120 in acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 2 1: yeast culture of Saccharomyces brasiliensis KCh 905 / acetone / 24 h / 25 °C / Microbiological reaction 2: yeast culture of Candida viswanathii KCh 120 / acetone / 216 h / 25 °C / Microbiological reaction With yeast culture of Saccharomyces brasiliensis KCh 905, yeast culture of Candida viswanathii KCh 120 in acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 2

204/258

2018-07-03 17:29:03

1: yeast culture of Saccharomyces cerevisiae KCh 464 / acetone / 144 h / 25 °C / Microbiological reaction 2: yeast culture of Candida viswanathii KCh 120 / acetone / 216 h / 25 °C / Microbiological reaction With yeast culture of Saccharomyces cerevisiae KCh 464, yeast culture of Candida viswanathii KCh 120 in acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 2 1: yeast culture of Yarrowia lipolytica ATCC 32-338 A / acetone / 72 h / 25 °C / Microbiological reaction 2: yeast culture of Candida viswanathii KCh 120 / acetone / 216 h / 25 °C / Microbiological reaction With yeast culture of Yarrowia lipolytica ATCC 32-338 A, yeast culture of Candida viswanathii KCh 120 in acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 3 1: yeast culture of Candida viswanathii KCh 120 / acetone / 144 h / 25 °C / Microbiological reaction 2: sodium tetrahydroborate / methanol 3: yeast culture of Candida parapsilosis KCh 909 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 3 1: yeast culture of Candida viswanathii KCh 120 / acetone / 6 h / 25 °C / Microbiological reaction 2: sodium tetrahydroborate / methanol 3: yeast culture of Candida parapsilosis KCh 909 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 3 1: yeast culture of Rhodotorula glutinis KCh 242 / acetone / 6 h / 25 °C / Microbiological reaction 2: sodium tetrahydroborate / methanol 3: yeast culture of Candida parapsilosis KCh 909 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 3 1: yeast culture of Rhodotorula rubra KCh 4 / acetone / 24 h / 25 °C / Microbiological reaction 2: sodium tetrahydroborate / methanol 3: yeast culture of Candida parapsilosis KCh 909 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 3 1: yeast culture of Rhodotorula rubra KCh 82 / acetone / 24 h / 25 °C / Microbiological reaction 2: sodium tetrahydroborate / methanol 3: yeast culture of Candida parapsilosis KCh 909 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 3 1: yeast culture of Rhodotorula rubra KCh 82 / acetone / 6 h / 25 °C / Microbiological reaction 2: sodium tetrahydroborate / methanol 3: yeast culture of Candida parapsilosis KCh 909 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone

205/258

2018-07-03 17:29:03

Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 3 1: yeast culture of Saccharomyces brasiliensis KCh 905 / acetone / 24 h / 25 °C / Microbiological reaction 2: sodium tetrahydroborate / methanol 3: yeast culture of Candida parapsilosis KCh 909 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 3 1: yeast culture of Saccharomyces cerevisiae KCh 464 / acetone / 144 h / 25 °C / Microbiological reaction 2: sodium tetrahydroborate / methanol 3: yeast culture of Candida parapsilosis KCh 909 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys Reaction Steps: 3 1: yeast culture of Yarrowia lipolytica ATCC 32-338 A / acetone / 72 h / 25 °C / Microbiological reaction 2: sodium tetrahydroborate / methanol 3: yeast culture of Candida parapsilosis KCh 909 / acetone / 216 h / 25 °C / Microbiological reaction With sodium tetrahydroborate in methanol, acetone Janeczko, Tomasz; Kostrzewa-Suslow, Edyta; Tetrahedron Asymmetry; vol. 25; nb. 18-19; (2014); p. 1264 - 1269 View in Reaxys HO

H HO

Rx-ID: 39446289 View in Reaxys 52/176 Yield

Conditions & References With C25H30N4O in diethyl ether, Time= 168h, T= -50 °C Ma, Gaoyuan; Deng, Jun; Sibi, Mukund P.; Angewandte Chemie - International Edition; vol. 53; nb. 44; (2014); p. 11818 11821; Angew. Chem.; vol. 53-126; nb. 44; (2014); p. 12180 View in Reaxys

H HO

Rx-ID: 39446337 View in Reaxys 53/176

206/258

2018-07-03 17:29:03

Yield

Conditions & References With sodium hydroxide in methanol, Time= 0.333333h Ma, Gaoyuan; Deng, Jun; Sibi, Mukund P.; Angewandte Chemie - International Edition; vol. 53; nb. 44; (2014); p. 11818 11821; Angew. Chem.; vol. 53-126; nb. 44; (2014); p. 12180 View in Reaxys

O O

H HO

Rx-ID: 1990769 View in Reaxys 54/176 Yield

Conditions & References With water, Time= 168h, T= 30 °C , asymmetric hydrolysis and resolution by Pseudomonas cepacia, Product distribution Horiuchi, Kenichi; Kobashi, Kazunori; Nagata, Hidetomo; Satoh, Toshinobu; Suemitsu, Rikisaku; Bioscience, Biotechnology, and Biochemistry; vol. 58; nb. 7; (1994); p. 1330 - 1331 View in Reaxys With phosphate buffer in diethyl ether, Time= 35h, Ambient temperature, bovine liver acetone powder (BLAP), Yield given. Yields of byproduct given. Title compound not separated from byproducts Basavaiah, Deevi; Krishna, Peddinti Rama; Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry; vol. 32; nb. 1; (1993); p. 131 - 134 View in Reaxys With water, Triton X-100, Time= 44h, T= 37 °C , nutrient broth containing Bacillus subtilis var. niger (IFO 3108), Yield given. Yields of byproduct given. Title compound not separated from byproducts Sugai, Takeshi; Kuwahara, Shigefumi; Hoshino, Chimaki; Matsuo, Noritada; Mori, Kenji; Agricultural and Biological Chemistry; vol. 46; nb. 10; (1982); p. 2579 - 2586 View in Reaxys With p-nitrobenzyl esterase from Bacillus subtilis in aq. phosphate buffer, ethanol, Time= 1.5h, Enzymatic reaction Zheng, Gao-Wei; Liu, Xu-Yun; Zhang, Zhi-Jun; Tian, Ping; Lin, Guo-Qiang; Xu, Jian-He; RSC Advances; vol. 3; nb. 43; (2013); p. 20446 - 20449 View in Reaxys

H HO

Rx-ID: 37591531 View in Reaxys 55/176 Yield

Conditions & References Asymmetric transfer hydrogenation reaction; general procedure General procedure: Cinchona alkaloid was added to [Ru(COD)Cl2]n in dry degassedi-PrOH (10 mL) and stirred at room temperature for 30 min under argon. The base was added and the reaction mixture was stirred for another 30 min. The aromatic ketone

207/258

2018-07-03 17:29:03

was then added in one portion(0.1 M) and the reduction was conducted at the given temperature for the time indicated. After completion of the reaction, the resulting solution was neutralised, and then extracted with Et2O. The organic phase was dried over MgSO4 and the conversion and enantiomeric excess were determined by GC analysis according to the literature.4,16– 18(S)-(−)-1-Phenylethanol: Table 4, entry 1; 83percent yield, 90percent ee (S),[η]25D = −45.0 (c 1.0, CH2Cl2) [lit.4, [η]23D = −50.0 (c 1.0, CH2Cl2)]. 1H NMR(400 M, CDCl3), η 1.40–1.55 (m, 3H), 1.90 (s, 1H), 4.95 (d, J = 6.3 Hz,1H), 7.20–7.65 (m, 5H). GC η-DEX120 capillary column, column temperature: 115 °C, t (R) = 12.7 min, t (S) = 13.5 min.(S)-(−)-1-Phenyl-1-propanol: Table 4, entry 2; 98percent yield, 86percent ee (S),[η]25D = −30.5 (c 5.0, EtOH) [lit.4, [η]23D = −34.0 (c 5.03, EtOH)]. 1H NMR(400 M, CDCl3),η 1.15–1.25 (m, 3H), 1.69 (s, 1H), 1.72–1.92 (m, 2H), 4.61(d, J = 4.5 Hz, 1H), 7.20–7.56 (m, 5H). GC η-DEX120 capillary column, column temperature: 115 °C, t (R) = 14.5 min, t (S) = 15.9 min. Stage 1: With dichloro(1,5-cyclooctadiene)ruthenium(II), (R)-(6-methoxyquinolin-4-yl)((1S,2R,4S,5R)-5-vinylquinuclidin-2yl)methanamine, Time= 0.5h, T= 20 °C , Inert atmosphere Stage 2: With potassium hydroxide, Time= 0.5h, Inert atmosphere Stage 3:, Time= 96h, T= 0 °C , Inert atmosphere, enantioselective reaction Jiang, Heyan; Journal of Chemical Research; vol. 37; nb. 12; (2013); p. 761 - 763 View in Reaxys

H HO

Rx-ID: 11272682 View in Reaxys 56/176 Yield

Conditions & References With benzoic acid anhydride, N-ethyl-N,N-diisopropylamine in dichloromethane, Time= 12h, T= 20 °C , Title compound not separated from byproducts. Shiina, Isamu; Nakata, Kenya; Tetrahedron Letters; vol. 48; nb. 47; (2007); p. 8314 - 8317 View in Reaxys With N-ethyl-N,N-diisopropylamine in dichloromethane, Time= 12h, T= 20 °C , Title compound not separated from byproducts. Shiina, Isamu; Nakata, Kenya; Tetrahedron Letters; vol. 48; nb. 47; (2007); p. 8314 - 8317 View in Reaxys With (R)-(-)-benzotetramisole, benzoic acid anhydride, N-ethyl-N,N-diisopropylamine in dichloromethane, Time= 12h, T= 20 °C , optical yield given as percent ee, enantioselective reaction Shiina, Isamu; Nakata, Kenya; Sugimoto, Masuhiro; Onda, Yu-Suke; Iizumi, Takashi; Ono, Keisuke; Heterocycles; vol. 77; nb. 2; (2009); p. 801 - 810 View in Reaxys With (R)-9-methyl-2-phenyl-9-hydro-2-imidazolino[1,2-a]benzimidazole, 2,2-dimethylpropanoic anhydride in diethyl ether, Time= 12h, T= 20 °C , Resolution of racemate, optical yield given as percent ee Nakata, Kenya; Shiina, Isamu; Organic and Biomolecular Chemistry; vol. 9; nb. 20; (2011); p. 7092 - 7096 View in Reaxys With (R)-(-)-benzotetramisole, nicotinic anhydride in dichloromethane, Time= 12h, T= -45 °C , Inert atmosphere, Resolution of racemate, Reagent/catalyst, Temperature, Overall yield = 89 percent; enantioselective reaction Shiina, Isamu; Nakata, Kenya; Ono, Keisuke; Mukaiyama, Teruaki; Helvetica Chimica Acta; vol. 95; nb. 10; (2012); p. 1891 - 1911,21

208/258

2018-07-03 17:29:03

View in Reaxys Shiina, Isamu; Nakata, Kenya; Ono, Keisuke; Mukaiyama, Teruaki; Helvetica Chimica Acta; vol. 95; nb. 10; (2012); p. 1891 - 1911 View in Reaxys With nicotinic anhydride, (+)-(R,S)-Fused-BTM in dichloromethane, Time= 12h, T= 0 °C , Inert atmosphere, Resolution of racemate, Reagent/catalyst, enantioselective reaction Shiina, Isamu; Nakata, Kenya; Ono, Keisuke; Mukaiyama, Teruaki; Helvetica Chimica Acta; vol. 95; nb. 10; (2012); p. 1891 - 1911,21 View in Reaxys Shiina, Isamu; Nakata, Kenya; Ono, Keisuke; Mukaiyama, Teruaki; Helvetica Chimica Acta; vol. 95; nb. 10; (2012); p. 1891 - 1911 View in Reaxys

H OH

Rx-ID: 29037147 View in Reaxys 57/176 Yield

Conditions & References With Pseudomonas monteilii TA-5 in methanol, Time= 0.5h, T= 30 °C , pH= 7, aq. phosphate buffer, optical yield given as percent ee, enantioselective reaction Chen, Yongzheng; Lie, Felicia; Li, Zhi; Advanced Synthesis and Catalysis; vol. 351; nb. 13; (2009); p. 2107 - 2112 View in Reaxys With ethylenediaminetetraacetic acid, Agrocybe aegerita aromatic peroxygenase, oxygen, Flavin mononucleotide, T= 20 °C , pH= 7, aq. phosphate buffer, Irradiation, Enzymatic reaction, optical yield given as percent ee, enantiospecific reaction Churakova, Ekaterina; Kluge, Martin; Ullrich, Rene; Arends, Isabel; Hofrichter, Martin; Hollmann, Frank; Angewandte Chemie - International Edition; vol. 50; nb. 45; (2011); p. 10716 - 10719 View in Reaxys With Agrocybe aegerita peroxygenase, dihydrogen peroxide in water, acetonitrile, Time= 0.166667h, pH= 7, potassium phosphate buffer, Enzymatic reaction, optical yield given as percent ee, enantioselective reaction Kluge, Martin; Ullrich, Rene; Scheibner, Katrin; Hofrichter, Martin; Green Chemistry; vol. 14; nb. 2; (2012); p. 440 - 446 View in Reaxys

99 %Chromat.

With mycelia of Aspergillus flavus MTCC-1783, Time= 24h, T= 30 °C , Enzymatic reaction, optical yield given as percent ee, stereoselective reaction Yadav, Saroj; Yadav; Canadian Journal of Chemistry; vol. 90; nb. 7; (2012); p. 597 - 599 View in Reaxys HO

H HO

Rx-ID: 29257559 View in Reaxys 58/176 Yield 43 %

209/258

2018-07-03 17:29:03

Nakata, Kenya; Shiina, Isamu; Heterocycles; vol. 80; nb. 1; (2010); p. 169 - 175 View in Reaxys 43 %

With (R)-(-)-benzotetramisole, nicotinic anhydride in dichloromethane, Time= 12h, T= 0 °C , Inert atmosphere, Resolution of racemate, Reagent/catalyst, enantioselective reaction Shiina, Isamu; Nakata, Kenya; Ono, Keisuke; Mukaiyama, Teruaki; Helvetica Chimica Acta; vol. 95; nb. 10; (2012); p. 1891 - 1911,21 View in Reaxys Shiina, Isamu; Nakata, Kenya; Ono, Keisuke; Mukaiyama, Teruaki; Helvetica Chimica Acta; vol. 95; nb. 10; (2012); p. 1891 - 1911 View in Reaxys O HO

H HO

Rx-ID: 29257560 View in Reaxys 59/176 Yield 43 %

Conditions & References With (R)-(-)-benzotetramisole, nicotinic anhydride in dichloromethane, Time= 12h, T= 0 °C , Resolution of racemate, optical yield given as percent ee, enantioselective reaction Nakata, Kenya; Shiina, Isamu; Heterocycles; vol. 80; nb. 1; (2010); p. 169 - 175 View in Reaxys

43 %

41 %

With (R)-(-)-benzotetramisole, 2,2-dimethylpropanoic anhydride, N-ethyl-N,N-diisopropylamine in dichloromethane, Time= 12h, T= 20 °C , optical yield given as percent ee, enantioselective reaction Shiina, Isamu; Nakata, Kenya; Sugimoto, Masuhiro; Onda, Yu-Suke; Iizumi, Takashi; Ono, Keisuke; Heterocycles; vol. 77; nb. 2; (2009); p. 801 - 810 View in Reaxys

38 %

With (R)-9-methyl-2-phenyl-9-hydro-2-imidazolino[1,2-a]benzimidazole, 2,2-dimethylpropanoic anhydride in diethyl ether, Time= 12h, T= 20 °C , Resolution of racemate, optical yield given as percent ee Nakata, Kenya; Shiina, Isamu; Organic and Biomolecular Chemistry; vol. 9; nb. 20; (2011); p. 7092 - 7096 View in Reaxys

210/258

2018-07-03 17:29:03

HO O

H HO

Rx-ID: 29257567 View in Reaxys 60/176 Yield

Conditions & References

40 %

With (R)-(-)-benzotetramisole, nicotinic anhydride in dichloromethane, Time= 12h, T= 0 °C , Resolution of racemate, optical yield given as percent ee, enantioselective reaction Nakata, Kenya; Shiina, Isamu; Heterocycles; vol. 80; nb. 1; (2010); p. 169 - 175 View in Reaxys

40 %

HO O O

O O

H HO

Rx-ID: 29257568 View in Reaxys 61/176 Yield 45 %

Conditions & References With (R)-(-)-benzotetramisole, nicotinic anhydride in dichloromethane, Time= 12h, T= 0 °C , Inert atmosphere, Resolution of racemate, Reagent/catalyst, enantioselective reaction Shiina, Isamu; Nakata, Kenya; Ono, Keisuke; Mukaiyama, Teruaki; Helvetica Chimica Acta; vol. 95; nb. 10; (2012); p. 1891 - 1911,21 View in Reaxys Shiina, Isamu; Nakata, Kenya; Ono, Keisuke; Mukaiyama, Teruaki; Helvetica Chimica Acta; vol. 95; nb. 10; (2012); p. 1891 - 1911 View in Reaxys With (R)-(-)-benzotetramisole, nicotinic anhydride in dichloromethane, Time= 12h, T= 0 °C , Resolution of racemate, optical yield given as percent ee, enantioselective reaction Nakata, Kenya; Shiina, Isamu; Heterocycles; vol. 80; nb. 1; (2010); p. 169 - 175 View in Reaxys

211/258

2018-07-03 17:29:03

O H HO

Rx-ID: 29257569 View in Reaxys 62/176 Yield

Conditions & References

44 %

34 %

H HO

Rx-ID: 29257570 View in Reaxys 63/176 Yield 45 %

Conditions & References With (R)-(-)-benzotetramisole, nicotinic anhydride in dichloromethane, Time= 12h, T= 0 °C , Inert atmosphere, Resolution of racemate, Temperature, Reagent/catalyst, enantioselective reaction

212/258

2018-07-03 17:29:03

Shiina, Isamu; Nakata, Kenya; Ono, Keisuke; Mukaiyama, Teruaki; Helvetica Chimica Acta; vol. 95; nb. 10; (2012); p. 1891 - 1911,21 View in Reaxys Shiina, Isamu; Nakata, Kenya; Ono, Keisuke; Mukaiyama, Teruaki; Helvetica Chimica Acta; vol. 95; nb. 10; (2012); p. 1891 - 1911 View in Reaxys 44 %

With (R)-(-)-benzotetramisole, nicotinic anhydride in dichloromethane, Time= 12h, T= 0 °C , Resolution of racemate, Mechanism, Temperature, Reagent/catalyst, optical yield given as percent ee, enantioselective reaction Nakata, Kenya; Shiina, Isamu; Heterocycles; vol. 80; nb. 1; (2010); p. 169 - 175 View in Reaxys

43 %

With (R)-9-methyl-2-phenyl-9-hydro-2-imidazolino[1,2-a]benzimidazole, 2,2-dimethylpropanoic anhydride in ethyl acetate, Time= 12h, T= 20 °C , Resolution of racemate, optical yield given as percent ee Nakata, Kenya; Shiina, Isamu; Organic and Biomolecular Chemistry; vol. 9; nb. 20; (2011); p. 7092 - 7096 View in Reaxys

42 %

H HO

Rx-ID: 29257571 View in Reaxys 64/176 Yield 47 %

Conditions & References With (R)-9-methyl-2-phenyl-9-hydro-2-imidazolino[1,2-a]benzimidazole, 2,2-dimethylpropanoic anhydride in diethyl ether, Time= 12h, T= 20 °C , Resolution of racemate, optical yield given as percent ee Nakata, Kenya; Shiina, Isamu; Organic and Biomolecular Chemistry; vol. 9; nb. 20; (2011); p. 7092 - 7096 View in Reaxys

39 %

36 %

213/258

2018-07-03 17:29:03

View in Reaxys Shiina, Isamu; Nakata, Kenya; Ono, Keisuke; Mukaiyama, Teruaki; Helvetica Chimica Acta; vol. 95; nb. 10; (2012); p. 1891 - 1911 View in Reaxys HO

H HO

Rx-ID: 32836888 View in Reaxys 65/176 Yield

Conditions & References

86 %

With lipase B from Candida antarctica in cyclohexane, Time= 0.75h, T= 50 °C , Resolution of racemate, optical yield given as percent ee Li, Xiang; Shi, Yi; Wang, Zhoujun; Zhang, Yahong; Tang, Yi; Journal of Catalysis; vol. 288; (2012); p. 24 - 32 View in Reaxys

H HO

Rx-ID: 33778054 View in Reaxys 66/176 Yield

Conditions & References

33 %

With Toyonite-200M-supported Burkholderia cepacia lipase I287F/I290A mutant in di-isopropyl ether, Time= 50h, T= 30 °C , Molecular sieve, Enzymatic reaction, optical yield given as percent ee, enantioselective reaction Ema, Tadashi; Nakano, Yasuko; Yoshida, Daiki; Kamata, Shusuke; Sakai, Takashi; Organic and Biomolecular Chemistry; vol. 10; nb. 31; (2012); p. 6299 - 6308 View in Reaxys

H HO

Rx-ID: 34257960 View in Reaxys 67/176 Yield

Conditions & References With nicotinic anhydride, (-)-(S)-η-Np-BTM in dichloromethane, Time= 12h, T= 0 °C , Inert atmosphere, Resolution of racemate, Reagent/catalyst, enantioselective reaction

214/258

2018-07-03 17:29:03

HO O

O O

O HO

O O

O OH

Rx-ID: 34605493 View in Reaxys 68/176 Yield

Conditions & References

10 %

With lipase from candida antartica in aq. phosphate buffer, Time= 48h, T= 30 °C Kataoka, Noriyuki; Okudomi, Masayuki; Chihara, Naoka; Matsumoto, Kazutsugu; Letters in Organic Chemistry; vol. 9; nb. 9; (2012); p. 615 - 621 View in Reaxys

H OH

Rx-ID: 34605495 View in Reaxys 69/176 Yield

Conditions & References

17 %

HO HO

O O

Rx-ID: 34605537 View in Reaxys 70/176

215/258

2018-07-03 17:29:03

Yield

Conditions & References Reaction Steps: 2 1: dmap / dichloromethane / 20 °C / Inert atmosphere 2: lipase from candida antartica / aq. phosphate buffer / 48 h / 30 °C With dmap, lipase from candida antartica in aq. phosphate buffer, dichloromethane Kataoka, Noriyuki; Okudomi, Masayuki; Chihara, Naoka; Matsumoto, Kazutsugu; Letters in Organic Chemistry; vol. 9; nb. 9; (2012); p. 615 - 621 View in Reaxys HO

H OH

Rx-ID: 34605538 View in Reaxys 71/176 Yield

H H

Rx-ID: 4568340 View in Reaxys 72/176 Yield

Conditions & References With lithium aluminium tetrahydride in diethyl ether, Time= 6h, Heating Naemura, Koichiro; Murata, Masaki; Tanaka, Rie; Yano, Masashi; Hirose, Keiji; Tobe, Yoshito; Tetrahedron Asymmetry; vol. 7; nb. 11; (1996); p. 3285 - 3294 View in Reaxys With sodium hydroxide in methanol, Time= 0.0833333h, Heating Spivey, Alan C.; Arseniyadis, Stellios; Fekner, Tomasz; Maddaford, Adrian; Leese, David P.; Tetrahedron; vol. 62; nb. 2-3; (2006); p. 295 - 301 View in Reaxys 4.4. General procedure for the green resolution of chiral alcohols General procedure: A 25 ml round-bottom flask was charged with 1 mmol racemic secondary alcohol, 5 mL vinyl acetate. Then 10 mg of immobilized enzyme was added in the previous mixture. When this was completed, the resulting mixture was stirred at ambient temperature for a certain time. Conversions and ee values were determined by GC analysis or HPLC analysis. When the reaction was complete, the solution was filtered through a pad of cotton; the solvent and the unreacted vinyl acetate were removed in vacuum. The resulting residues were purified by chromatography on silica gel with petroleum ether-ethyl acetate (1:10-1:5) to afford the corresponding pure (R)-configured esters. A 25 ml round-bottom flask was charged with the (R)-ester of

216/258

2018-07-03 17:29:03

0.5 mmol, 10 mL isopropyl ether and immobilized CALB (Novozym 435) recycled from the former round or new addition, sealed and anhydrous ammonia was added to the solution. The resulting mixture was stirred at 35 °C for a certain time. Samples were taken at 1 h intervals, each time 20 μl of solution were used for analyzing. When the reaction was complete, the solution was filtered through a pad of cotton and the solvent was removed in vacuo. The resulting residues were purified by chromatography on silica gel with petroleum ether-ethyl acetate (1:1-1:5) to afford the corresponding (R)-alcohols; the ee values of the desired products are summarized in Table 5. With immobilized CALB lipase, ammonia in di-isopropyl ether, Time= 13h, T= 35 °C , Enzymatic reaction, optical yield given as percent ee, enantioselective reaction Wang, Bo; Jiang, Ling; Wang, Jue; Ma, Jingbo; Liu, Min; Yu, Hongwei; Tetrahedron Asymmetry; vol. 22; nb. 9; (2011); p. 980 - 985 View in Reaxys HO

H HO

Rx-ID: 11272686 View in Reaxys 73/176 Yield

O B

H OH

Rx-ID: 28856797 View in Reaxys 74/176 Yield

Conditions & References With sodium perborate, water in tetrahydrofuran, T= 22 °C Noh, Dongwan; Chea, Heesung; Ju, Junghwan; Yun, Jaesook; Angewandte Chemie, International Edition; vol. 48; nb. 33; (2009); p. 6062 - 6064; Angewandte Chemie; vol. 121; nb. 33; (2009); p. 6178 - 6180

217/258

2018-07-03 17:29:03

View in Reaxys With sodium perborate, water in tetrahydrofuran, T= 20 °C , Inert atmosphere Noh, Dongwan; Yoon, Sue Kyoung; Won, Jiyeon; Lee, Jin Yong; Yun, Jaesook; Chemistry - An Asian Journal; vol. 6; nb. 8; (2011); p. 1967 - 1969 View in Reaxys

H HO

Rx-ID: 30068416 View in Reaxys 75/176 Yield

Conditions & References With Candida antarctica lipase B W104A in toluene, Time= 24h, T= 60 °C , Resolution of racemate, Inert atmosphere, optical yield given as percent ee, enantioselective reaction Engstroem, Karin; Vallin, Michaela; Syren, Per-Olof; Hult, Karl; Baeckvall, Jan-E.; Organic and Biomolecular Chemistry; vol. 9; nb. 1; (2011); p. 81 - 82 View in Reaxys

(v2)

H O

Rx-ID: 30130961 View in Reaxys 76/176 Yield

Conditions & References With titanium(IV) isopropylate, C2HF3O2*C27H23NO4 in acetonitrile, Time= 1.5h, T= -40 - 0 °C , optical yield given as percent ee, enantioselective reaction Von Roenn, Robert; Christoffers, Jens; Tetrahedron; vol. 67; nb. 2; (2011); p. 334 - 338 View in Reaxys

H OH

Rx-ID: 30733705 View in Reaxys 77/176 Yield 95 %Chromat.

Conditions & References With C39H31Cl2N4OPRu, potassium isopropoxide, Time= 0.75h, T= 28 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Ye, Wenjing; Zhao, Miao; Du, Wangming; Jiang, Quanbin; Wu, Kaikai; Wu, Ping; Yu, Zhengkun; Chemistry - A European Journal; vol. 17; nb. 17; (2011); p. 4737 - 4741 View in Reaxys

HO B

H HO

Rx-ID: 31264572 View in Reaxys 78/176

218/258

2018-07-03 17:29:03

Yield

Conditions & References

63 %

With CH2CH2O(C10H5O)4H2P2N2(CH3)4, (p-cymene)ruthenium(II) chloride, potassium carbonate in water, toluene, Time= 16h, T= 60 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Yamamoto, Yasunori; Shirai, Tomohiko; Watanabe, Momoko; Kurihara, Kazunori; Miyaura, Norio; Molecules; vol. 16; nb. 6; (2011); p. 5020 - 5034 View in Reaxys HO

Rx-ID: 31730453 View in Reaxys 79/176 Yield

Conditions & References

50 %

Rx-ID: 31730463 View in Reaxys 80/176 Yield

Conditions & References

38 %

With 2,2-dimethylpropanoic anhydride, Levamisole in diethyl ether, Time= 12h, T= 20 °C , Resolution of racemate, optical yield given as percent ee Nakata, Kenya; Shiina, Isamu; Organic and Biomolecular Chemistry; vol. 9; nb. 20; (2011); p. 7092 - 7096 View in Reaxys H (v2)

219/258

2018-07-03 17:29:03

H OH

Rx-ID: 32015882 View in Reaxys 81/176 Yield

Conditions & References

19 %, 80 %

II.7 :Examples II-1 to II-7; Optimization of the Reagent Equivalents; The equivalents of zinc acetylide were subsequently optimized to achieve a better enantioselectivity with the toluene-THF (1.5:1) mixed solvent system according to Scheme II and the parameters of Table II. TABLE II 3 4 Example R x y Time (h)Yielda (percent)eeb (percent)yieldc (percent) II-1 Me 1.5 1.5 36 93 70 ND II-2 Me 2 2 36 98 69 ND II-3 Me 4 4 28 85 82 ND II-4 Me 8 8 36 94 81 ND II-5 Me 4 8 21 91 80 ND II-6 Me 4 2 48 85 81 ND II-7 Et 4 4 22 80 79 19 aIsolated yield after column chromatographybDetermination by chiral HPLC.cYield determined by crude 1H NMR. ND: not detected by 1H NMR.In accordance with the results of Table II, the reaction gave better ee when more than 4 equiv of organozincs were used (Examples II-1 and II-2 vs Examples II-3 to II-7). Although it was reported that a 1:1 mixture of alkynyl and dialkylzinc gave the propargylic alcohols in higher ee, adducts with comparable ee's were observed in these cases under different ratios of dimethylzinc to phenylacetylene (Examples II-3, II-5, and II-6). Alkylation product 4b was obtained when dimethylzinc was substituted with diethylzinc (Example II-7). Accordingly, 4 equiv of methylalkynylzinc for economical concern were applied for further optimization of solvents (Example II-3).; Stage 1: With (1S,4R)-(7,7-dimethyl-2-morpholin-4-yl-bicyclo[2.2.1]hept-1-yl)methanethiol in tetrahydrofuran, toluene, Time= 2h, T= 20 °C Stage 2: in tetrahydrofuran, toluene, Time= 22h, T= 0 °C Patent; UANG, Biing-Jiun; Wu, Ping-Yu; Wu, Hsyueh-Liang; US2011/295042; (2011); (A1) English View in Reaxys

H O

Rx-ID: 32115462 View in Reaxys 82/176 Yield

Conditions & References Stage 1: With magnesium in diethyl ether, Inert atmosphere Stage 2: With titanium(IV) isopropylate, (Sa)-2'-[(R)-hydroxy(phenyl)methyl]-(1,1'-binaphthalen)-2-ol in toluene, Time= 4.16h, T= -40 °C , Inert atmosphere, Grignard reaction, optical yield given as percent ee, enantioselective reaction Fernandez-Mateos, Emilio; MacIa, Beatriz; Ramon, Diego J.; Yus, Miguel; European Journal of Organic Chemistry; nb. 34; (2011); p. 6851 - 6855 View in Reaxys

H HO

Rx-ID: 1763946 View in Reaxys 83/176

220/258

2018-07-03 17:29:03

Yield

Conditions & References With sodium hydroxide, ((1R,2S,3R,5R)-2,6,6-trimethylbicyclo[3.1.1]heptan-3-yl)borane, dihydrogen peroxide, 1) THF, -25 deg C, 9 h, 2) 50 deg C, 1 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Brown, Herbert C.; Jadhav, Prabhakar K.; Journal of Organic Chemistry; vol. 46; nb. 24; (1981); p. 5047 - 5048 View in Reaxys With potassium fluoride, trichlorosilane, dihydrogen peroxide, potassium hydrogencarbonate, bis(η3-allyl-μ-chloropalladium(II)), (S)-[1,1'-binaphthalen]-2-yldiphenylphosphine, 1) 20 deg C, 7 d, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Kitayama, Kenji; Uozumi, Yasuhiro; Hayashi, Tamio; Journal of the Chemical Society, Chemical Communications; nb. 15; (1995); p. 1533 - 1534 View in Reaxys With sodium hydroxide, (R)-1-(2-diphenylphosphino-1-naphthyl)phenanthridine rhodium, dihydrogen peroxide, benzo[1,3,2]dioxaborole, 1.) THF, RT, 2 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Valk, Jean Marc; Whitlock, Gavin A.; Layzell, Timothy P.; Brown, John M.; Tetrahedron: Asymmetry; vol. 6; nb. 10; (1995); p. 2593 - 2596 View in Reaxys With sodium hydroxide, (S)-1-(2-diphenylphosphino-1-naphthyl)isoquinoline rhodium, dihydrogen peroxide, benzo[1,3,2]dioxaborole, 1.) THF, RT, 2 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Valk, Jean Marc; Whitlock, Gavin A.; Layzell, Timothy P.; Brown, John M.; Tetrahedron: Asymmetry; vol. 6; nb. 10; (1995); p. 2593 - 2596 View in Reaxys Stage 1: With benzo[1,3,2]dioxaborole, rhodium complex 2 in toluene, Time= 2h, T= 20 °C , Addition, Hydroboration Stage 2: With sodium hydroxide, water, dihydrogen peroxide in toluene, Time= 2h, T= 20 °C , Oxidation, Title compound not separated from byproducts Doucet, Henri; Fernandez, Elena; Layzell, Timothy P.; Brown, John M.; Chemistry - A European Journal; vol. 5; nb. 4; (1999); p. 1320 - 1330 View in Reaxys With benzo[1,3,2]dioxaborole, [Rh(cod)(S)-(QUINAP)]BF4 in tetrahydrofuran, Time= 2h, T= 25 °C , Title compound not separated from byproducts Segarra, Anna M.; Guirado, Francesc; Claver, Carmen; Fernandez, Elena; Tetrahedron Asymmetry; vol. 14; nb. 12; (2003); p. 1611 - 1615 View in Reaxys With benzo[1,3,2]dioxaborole, [Rh(cod)(S)-(QUINAP)]BF4 in tetrahydrofuran, Time= 2h, T= 25 °C , Title compound not separated from byproducts. Segarra, Anna M.; Guerrero, Ramon; Claver, Carmen; Fernandez, Elena; Chemistry - A European Journal; vol. 9; nb. 1; (2003); p. 191 - 200 View in Reaxys Stage 1: With CF3O3S(1-)*C44H37N2PRh(1+), benzo[1,3,2]dioxaborole in tetrahydrofuran, T= 0 °C , Inert atmosphere Stage 2: With dihydrogen peroxide, sodium hydroxide in ethanol, water, T= 0 - 20 °C , optical yield given as percent ee, enantioselective reaction Maxwell, Aoife C.; Flanagan, Susan P.; Goddard, Richard; Guiry, Patrick J.; Tetrahedron Asymmetry; vol. 21; nb. 11-12; (2010); p. 1458 - 1473 View in Reaxys

221/258

2018-07-03 17:29:03

H HO

Rx-ID: 4423696 View in Reaxys 84/176 Yield

Conditions & References With sodium hydroxide, (S)-1-(2-diphenylphosphino-1-naphthyl)isoquinoline rhodium, dihydrogen peroxide, benzo[1,3,2]dioxaborole, 1.) THF, RT, 2 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Valk, Jean Marc; Whitlock, Gavin A.; Layzell, Timothy P.; Brown, John M.; Tetrahedron: Asymmetry; vol. 6; nb. 10; (1995); p. 2593 - 2596 View in Reaxys Stage 1: With benzo[1,3,2]dioxaborole, rhodium complex 2 in toluene, Time= 2h, T= 20 °C , Addition, Hydroboration Stage 2: With sodium hydroxide, water, dihydrogen peroxide in toluene, Time= 2h, T= 20 °C , Oxidation, Title compound not separated from byproducts Doucet, Henri; Fernandez, Elena; Layzell, Timothy P.; Brown, John M.; Chemistry - A European Journal; vol. 5; nb. 4; (1999); p. 1320 - 1330 View in Reaxys Stage 1: With CF3O3S(1-)*C41H38ClN2PRh(1+), benzo[1,3,2]dioxaborole in tetrahydrofuran, Time= 2h, T= 20 °C , Inert atmosphere Stage 2: With dihydrogen peroxide, sodium hydroxide in tetrahydrofuran, ethanol, water, Time= 1h, T= 0 - 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Fleming, William J.; Mueller-Bunz, Helge; Guiry, Patrick J.; European Journal of Organic Chemistry; nb. 31; (2010); p. 5996 - 6004 View in Reaxys

H HO

Rx-ID: 8613715 View in Reaxys 85/176 Yield

Conditions & References Stage 1: With trimethylsilyl trifluoromethanesulfonate, benzo[1,3,2]dioxaborole, acethylacetonato(1,5-cyclooctadiene)rhodium(I), (R)-1-(2-phenylquinazolin-4-yl)-2-(Ph2P)-naphthalene in tetrahydrofuran, Time= 2h, T= 25 °C , Addition, Hydroboration Stage 2: With sodium hydroxide, dihydrogen peroxide in tetrahydrofuran, Time= 1h, T= 20 °C , Oxidation, Hydrolysis, Further stages. Title compound not separated from byproducts. McCarthy, Mary; Hooper, Mark W.; Guiry, Patrick J.; Chemical Communications; nb. 14; (2000); p. 1333 - 1334 View in Reaxys Stage 1: With CF3O3S(1-)*C45H36F3N2PRh(1+), benzo[1,3,2]dioxaborole in tetrahydrofuran, T= 0 °C , Inert atmosphere Stage 2: With dihydrogen peroxide, sodium hydroxide in ethanol, water, T= 0 - 20 °C , optical yield given as percent ee, enantioselective reaction Maxwell, Aoife C.; Flanagan, Susan P.; Goddard, Richard; Guiry, Patrick J.; Tetrahedron Asymmetry; vol. 21; nb. 11-12; (2010); p. 1458 - 1473 View in Reaxys

222/258

2018-07-03 17:29:03

Stage 1: With CF3O3S(1-)*C41H38ClN2PRh(1+), benzo[1,3,2]dioxaborole in tetrahydrofuran, Time= 2h, T= 20 °C , Inert atmosphere Stage 2: With dihydrogen peroxide, sodium hydroxide in tetrahydrofuran, ethanol, water, Time= 1h, T= 0 - 20 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Fleming, William J.; Mueller-Bunz, Helge; Guiry, Patrick J.; European Journal of Organic Chemistry; nb. 31; (2010); p. 5996 - 6004 View in Reaxys HO

H HO

Rx-ID: 9657572 View in Reaxys 86/176 Yield

Conditions & References With (R)-5-CF3-2-Ph-2,3-dihydroimidazo[1,2-a]pyridine, N-ethyl-N,N-diisopropylamine in chloroform, Time= 8h, cooling, Title compound not separated from byproducts Birman, Vladimir B.; Uffman, Eric W.; Jiang, Hui; Li, Ximin; Kilbane, Corey J.; Journal of the American Chemical Society; vol. 126; nb. 39; (2004); p. 12226 - 12227 View in Reaxys Stage 1: With chiral 4-diethylaminopyridine-based reagent, triethylamine, Time= 9h, T= -78 °C Stage 2: in methanol, Time= 0.25h, T= -78 - 20 °C , Title compound not separated from byproducts Spivey, Alan C.; Arseniyadis, Stellios; Fekner, Tomasz; Maddaford, Adrian; Leese, David P.; Tetrahedron; vol. 62; nb. 2-3; (2006); p. 295 - 301 View in Reaxys With sodium sulfate, N-ethyl-N,N-diisopropylamine, (R)-(-)-benzotetramisole in chloroform-d1, Time= 4h, T= 20 °C , Title compound not separated from byproducts Birman, Vladimir B.; Li, Ximin; Organic Letters; vol. 8; nb. 7; (2006); p. 1351 - 1354 View in Reaxys A.1.1 :To a solution of 0.25 mmol of phenylethylcarbinol (34 L, 34 mg) and 0.050 mmol of the catalyst (2a-d) in 0.250 mL CDCl3 was added 0.25 mmol of acetic anhydride (24 L, 26 mg). The mixture was swirled, left at room temperature for 1 hour, quenched by rapid addition of 0.25 mL of methanol, and left for one more hour. The reaction mixture was diluted with CH2Cl2, washed twice with 1 M HCl, then twice with saturated aqueous NaHCO3, and dried over Na2SO4. The solution was concentrated on a rotary evaporator at room temperature and chromatographed (5-20percent Et2O in hexanes) to separate the ester from the unreacted alcohol. With (R)-2-phenyl-2,3-dihydroimidazo[1,2-a]pyridine in chloroform-d1, Time= 1h, T= 20 °C , Resolution of racemate, Product distribution / selectivity Patent; Birman, Vladimir; US2005/256150; (2005); (A1) English View in Reaxys A.1.4 :To a solution of 0.25 mmol of phenylethylcarbinol (34 L, 34 mg) and 0.050 mmol of the catalyst (2a-d) in 0.250 mL CDCl3 was added 0.25 mmol of acetic anhydride (24 L, 26 mg). The mixture was swirled, left at room temperature for 1 hour, quenched by rapid addition of 0.25 mL of methanol, and left for one more hour. The reaction mixture was diluted with CH2Cl2, washed twice with 1 M HCl, then twice with saturated aqueous NaHCO3, and dried over Na2SO4. The solution was concentrated on a rotary evaporator at room temperature and chromatographed (5-20percent Et2O in hexanes) to separate the ester from the unreacted alcohol.

223/258

2018-07-03 17:29:03

With (R)-5-trifluoromethyl-2-phenyl-2,3-dihydroimidazo[1,2-a]pyridine in chloroform-d1, Time= 1h, T= 20 °C , Resolution of racemate, Product distribution / selectivity Patent; Birman, Vladimir; US2005/256150; (2005); (A1) English View in Reaxys A.1.2 :To a solution of 0.25 mmol of phenylethylcarbinol (34 L, 34 mg) and 0.050 mmol of the catalyst (2a-d) in 0.250 mL CDCl3 was added 0.25 mmol of acetic anhydride (24 L, 26 mg). The mixture was swirled, left at room temperature for 1 hour, quenched by rapid addition of 0.25 mL of methanol, and left for one more hour. The reaction mixture was diluted with CH2Cl2, washed twice with 1 M HCl, then twice with saturated aqueous NaHCO3, and dried over Na2SO4. The solution was concentrated on a rotary evaporator at room temperature and chromatographed (5-20percent Et2O in hexanes) to separate the ester from the unreacted alcohol. With (R)-5-bromo-2-phenyl-2,3-dihydroimidazo[1,2-a]pyridine in chloroform-d1, Time= 1h, T= 20 °C , Resolution of racemate, Product distribution / selectivity Patent; Birman, Vladimir; US2005/256150; (2005); (A1) English View in Reaxys Stage 1: With (S,R(P))-2-phenyl-2,3-dihydroimidazo[1,2-a]pyrindinyl-pentaphenylcyclopentadienyliron, N-ethyl-N,N-diisopropylamine in toluene, Time= 0.0833333h, T= 0 °C Stage 2: in toluene, Time= 7h, T= 0 °C , optical yield given as percent ee, enantioselective reaction Hu, Bin; Meng, Meng; Wang, Zheng; Du, Wenting; Fossey, John S.; Hu, Xinquan; Deng, Wei-Ping; Journal of the American Chemical Society; vol. 132; nb. 47; (2010); p. 17041 - 17044 View in Reaxys HO

H HO

O O

Rx-ID: 9666721 View in Reaxys 87/176 Yield

224/258

2018-07-03 17:29:03

Birman, Vladimir B.; Li, Ximin; Organic Letters; vol. 8; nb. 7; (2006); p. 1351 - 1354 View in Reaxys With sodium sulfate, N-ethyl-N,N-diisopropylamine, (R)-(-)-benzotetramisole in chloroform, Time= 33h, T= 0 °C , Title compound not separated from byproducts Birman, Vladimir B.; Li, Ximin; Organic Letters; vol. 8; nb. 7; (2006); p. 1351 - 1354 View in Reaxys With N-ethyl-N,N-diisopropylamine in chloroform-d1, Time= 8h, T= 0 °C , Title compound not separated from byproducts. Birman, Vladimir B.; Jiang, Hui; Li, Ximin; Organic Letters; vol. 9; nb. 17; (2007); p. 3237 - 3240 View in Reaxys B.3.6 :Procedure B: Variation of the solvent 1) The stock solution of the catalyst was prepared by dissolving 0.040 mmol of 2d (10.6 mg) and 1.5 mmol of N,N-diisopropylethylamine (262]L, 194 mg) in the reaction solvent in a 2 mL volumetric test tube and bringing the volume to the mark. 2) A one-dram vial was charged with 0.5 mmol of (O)-phenyl ethyl carbinol and 0.500 mL of the stock solution of 2d cooled in an ice bath. After 15 minutes, 0.375 mmol of propionic anhydride was added. The mixture was swirled and left in the ice bath for 8 hours, at the end of which it was quenched by rapid addition of 0.5 mL of methanol, allowed to warm slowly and left for one more hour at room temperature. The workup and chromatography were carried out as described in Procedure A. With N-ethyl-N,N-diisopropylamine, (R)-5-trifluoromethyl-2-phenyl-2,3-dihydroimidazo[1,2-a]pyridine in acetonitrile, Time= 8.25h, T= 0 °C , Resolution of racemate, Product distribution / selectivity Patent; Birman, Vladimir; US2005/256150; (2005); (A1) English View in Reaxys Stage 1: With (S,R(P))-2-phenyl-2,3-dihydroimidazo[1,2-a]pyrindinyl-pentaphenylcyclopentadienyliron, N-ethyl-N,N-diisopropylamine in tetrahydrofuran, Time= 0.0833333h, T= 0 °C Stage 2: in tetrahydrofuran, Time= 7h, T= 0 °C , optical yield given as percent ee, enantioselective reaction Hu, Bin; Meng, Meng; Wang, Zheng; Du, Wenting; Fossey, John S.; Hu, Xinquan; Deng, Wei-Ping; Journal of the American Chemical Society; vol. 132; nb. 47; (2010); p. 17041 - 17044 View in Reaxys HO H

Mg H

Rx-ID: 29121175 View in Reaxys 88/176 Yield

Conditions & References

57 %, 31 %

Stage 1: With titanium(IV) isopropylate in dichloromethane, Time= 0.166667h, T= -78 °C , Inert atmosphere Stage 2: With (R)-3-(3,5-diphenylphenyl)-2,2'-dihydroxy-1,1'-binaphthyl in diethyl ether, dichloromethane, Time= 3h, T= 0 °C , Inert atmosphere Stage 3: With hydrogenchloride, water in diethyl ether, dichloromethane, T= 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Muramatsu, Yusuke; Kanehira, Shinichi; Tanigawa, Masato; Miyawaki, Yuta; Harada, Toshiro; Bulletin of the Chemical Society of Japan; vol. 83; nb. 1; (2010); p. 19 - 32 View in Reaxys

O O

(v1) (v1)

Pol O

225/258

2018-07-03 17:29:03

(v1)

H HO

Pol

Rx-ID: 29319903 View in Reaxys 89/176 Yield

Conditions & References With Porcine pancreas lipase type II, water in hexane, Time= 24h, T= 0 °C , pH= 6.5, aq. phosphate buffer, Resolution of racemate, solid phase reaction, Enzymatic reaction, optical yield given as percent ee, enantioselective reaction Okudomi, Masayuki; Shimojo, Megumi; Nogawa, Masaki; Hamanaka, Ayae; Taketa, Natsue; Nakagawa, Takuya; Matsumoto, Kazutsugu; Bulletin of the Chemical Society of Japan; vol. 83; nb. 2; (2010); p. 182 - 189 View in Reaxys

O O

O O (v1) (v1)

Pol

O O

OH (v1)

Pol O

Rx-ID: 29319905 View in Reaxys 90/176 Yield

(v2)

H HO

Rx-ID: 29349643 View in Reaxys 91/176 Yield

Conditions & References Stage 1: With C42H26N4O6Ru, dihydrogen peroxide in dichloromethane, T= 20 °C Stage 2: With titanium(IV)isopropoxide in dichloromethane, Time= 96h, T= -10 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction

226/258

2018-07-03 17:29:03

Chen, Xi; Liu, Qiang; Sun, Hong-Bao; Yu, Xiao-Qi; Pu, Lin; Tetrahedron Letters; vol. 51; nb. 17; (2010); p. 2345 - 2347 View in Reaxys

H HO

OH O

Rx-ID: 29753843 View in Reaxys 92/176 Yield

Conditions & References Stage 1: With dmap, dicyclohexyl-carbodiimide in dichloromethane, T= 20 °C , Inert atmosphere Stage 2: With immobilized Candida antarctica Lipase B, water in hexane, Time= 24h, T= 30 °C , pH= 6.5, aq. phosphate buffer, Enzymatic reaction, optical yield given as percent ee, enantioselective reaction Okudomi, Masayuki; Ageishi, Kanpei; Yamada, Tomomi; Chihara, Naoka; Nakagawa, Takuya; Mizuochi, Katsumi; Matsumoto, Kazutsugu; Tetrahedron; vol. 66; nb. 40; (2010); p. 8060 - 8067 View in Reaxys

O O

H HO

Rx-ID: 29758073 View in Reaxys 93/176 Yield 45 %, 46 %

Conditions & References With Pseudomonas fluorescence lipase, Resolution of racemate, Enzymatic reaction, optical yield given as percent ee Scholz, Roland; Hellmann, Gunther; Rohs, Susanne; Oezdemir, Diana; Raabe, Gerhard; Vermeeren, Cornelia; Gais, Hans-Joachim; European Journal of Organic Chemistry; nb. 24; (2010); p. 4588 - 4616 View in Reaxys

H HO

Rx-ID: 29790632 View in Reaxys 94/176 Yield

Conditions & References Stage 1: With CF3O3S(1-)*C45H39N2OPRh(1+), benzo[1,3,2]dioxaborole in tetrahydrofuran, T= 0 °C , Inert atmosphere Stage 2: With dihydrogen peroxide, sodium hydroxide in ethanol, water, T= 0 - 20 °C , optical yield given as percent ee, enantioselective reaction Maxwell, Aoife C.; Flanagan, Susan P.; Goddard, Richard; Guiry, Patrick J.; Tetrahedron Asymmetry; vol. 21; nb. 11-12; (2010); p. 1458 - 1473 View in Reaxys

227/258

2018-07-03 17:29:03

SiH O

H OH

Rx-ID: 29890954 View in Reaxys 95/176 Yield

Conditions & References With methanol, potassium carbonate in toluene, Time= 1h, T= 20 °C Issenhuth, Jean-Thomas; Dagorne, Samuel; Bellemin-Laponnaz, Stephane; Comptes Rendus Chimie; vol. 13; nb. 3; (2010); p. 353 - 357 View in Reaxys HO

H HO

Rx-ID: 30065973 View in Reaxys 96/176 Yield

O O

Rx-ID: 30065974 View in Reaxys 97/176 Yield

Conditions & References Stage 1: With (S,R(P))-2-phenyl-2,3-dihydroimidazo[1,2-a]pyrindinyl-pentaphenylcyclopentadienyliron, N-ethyl-N,N-diisopropylamine in chloroform, Time= 0.0833333h, T= 0 °C Stage 2: in chloroform, Time= 7h, T= 0 °C , optical yield given as percent ee, enantioselective reaction Hu, Bin; Meng, Meng; Wang, Zheng; Du, Wenting; Fossey, John S.; Hu, Xinquan; Deng, Wei-Ping; Journal of the American Chemical Society; vol. 132; nb. 47; (2010); p. 17041 - 17044 View in Reaxys

228/258

2018-07-03 17:29:03

H HO

O O

Rx-ID: 11272683 View in Reaxys 98/176 Yield

H HO

Rx-ID: 23663134 View in Reaxys 99/176 Yield

Conditions & References A.1.9; B.3.1; C.4.5 :To a solution of 0.25 mmol of phenylethylcarbinol (34 L, 34 mg) and 0.050 mmol of the catalyst (2a-d) in 0.250 mL CDCl3 was added 0.25 mmol of acetic anhydride (24 L, 26 mg). The mixture was swirled, left at room temperature for 1 hour, quenched by rapid addition of 0.25 mL of methanol, and left for one more hour. The reaction mixture was diluted with CH2Cl2, washed twice with 1 M HCl, then twice with saturated aqueous NaHCO3, and dried over Na2SO4. The solution was concentrated on a rotary evaporator at room temperature and chromatographed (5-20percent Et2O in hexanes) to separate the ester from the unreacted alcohol.; The reaction time is expressed in hours and is shown under t(h). Entries 14 in Table 1 were obtained using 20 mol percent of the catalyst in deuterated chloroform CDCl3 at room temperature for 1 hour, and entries 5-14 were obtained using 2 mol percent of the catalyst at 0° C. in the presence of N,N-diisopropylethylamine in chloroform CHCl3 for the specified period of time. The esters produced and the unreacted alcohols resulting from kinetic resolution experiments were analyzed by chiral HPLC to determine their enantiomeric excesses (see below). HPLC analyses were performed on a Breeze LC system (Waters Corporation) and CHIRALCEL OD-H analytical column (4.6x250 mm, Chiral Technologies, Inc.) using isopropanol-hexanes mobile phase at a flow rate of 1 mL/min and UV detection at 254 nm. Specific optical rotations were measured using a Perkin-Elmer 241 polarimeter. The absolute chirality of the esters and alcohols obtained by kinetic resolution was determined by the sign of the optical rotation of the unreacted alcohol.; Procedure B: Variation of the solvent 1) The stock solution of the catalyst was prepared by dissolving 0.040 mmol of 2d (10.6 mg) and 1.5 mmol of N,N-diisopropylethylamine (262]L, 194 mg) in the reaction solvent in a 2 mL volumetric test tube and bringing the volume to the mark. 2) A one-dram vial was charged with 0.5 mmol of (O)-phenyl ethyl carbinol and 0.500 mL of the stock solution of 2d cooled in an ice bath. After 15 minutes, 0.375 mmol of propionic anhydride was added. The mixture was swirled and left in the ice bath for 8 hours, at the end of which it was quenched by rapid addition of 0.5 mL of methanol, allowed to warm slowly and left for one more hour at room tempera-

229/258

2018-07-03 17:29:03

ture. The workup and chromatography were carried out as described in Procedure A.; Procedure C. Variation of the substrate and the acylating agent in the CF3PIP-catalyzed kinetic resolutions. 1) The stock solution of the catalyst was prepared by dissolving 0.100 mmol of 2d (26.4 mg) and 3.75 mmol of N,N-diisopropylethylamine (6540L, 485 mg) in CHCl3 in a 5 mL volumetric flask and bringing the volume to the mark. 2) A one-dram vial was charged with 0.5 mmol of the racemic secondary alcohol and 0.500 mL of the stock solution of 2d, and cooled in an ice bath. After 15 minutes, 0.375 mmol of the anhydride was added. The mixture was swirled and left in the ice bath for a specified period of time, at the end of which it was quenched by rapid addition of 0.5 mL of methanol, allowed to warm slowly and left for one more hour at room temperature. The workup and chromatography were carried out as described in Procedure A. With N-ethyl-N,N-diisopropylamine, (R)-5-trifluoromethyl-2-phenyl-2,3-dihydroimidazo[1,2-a]pyridine in chloroform, Time= 6 - 8.25h, T= 0 °C , Resolution of racemate, Product distribution / selectivity Patent; Birman, Vladimir; US2005/256150; (2005); (A1) English View in Reaxys B.3.4 :Procedure B: Variation of the solvent 1) The stock solution of the catalyst was prepared by dissolving 0.040 mmol of 2d (10.6 mg) and 1.5 mmol of N,N-diisopropylethylamine (262]L, 194 mg) in the reaction solvent in a 2 mL volumetric test tube and bringing the volume to the mark. 2) A one-dram vial was charged with 0.5 mmol of (O)-phenyl ethyl carbinol and 0.500 mL of the stock solution of 2d cooled in an ice bath. After 15 minutes, 0.375 mmol of propionic anhydride was added. The mixture was swirled and left in the ice bath for 8 hours, at the end of which it was quenched by rapid addition of 0.5 mL of methanol, allowed to warm slowly and left for one more hour at room temperature. The workup and chromatography were carried out as described in Procedure A. With N-ethyl-N,N-diisopropylamine, (R)-5-trifluoromethyl-2-phenyl-2,3-dihydroimidazo[1,2-a]pyridine in dichloromethane, Time= 8.25h, T= 0 °C , Resolution of racemate, Product distribution / selectivity Patent; Birman, Vladimir; US2005/256150; (2005); (A1) English View in Reaxys B.3.3 :Procedure B: Variation of the solvent 1) The stock solution of the catalyst was prepared by dissolving 0.040 mmol of 2d (10.6 mg) and 1.5 mmol of N,N-diisopropylethylamine (262]L, 194 mg) in the reaction solvent in a 2 mL volumetric test tube and bringing the volume to the mark. 2) A one-dram vial was charged with 0.5 mmol of (O)-phenyl ethyl carbinol and 0.500 mL of the stock solution of 2d cooled in an ice bath. After 15 minutes, 0.375 mmol of propionic anhydride was added. The mixture was swirled and left in the ice bath for 8 hours, at the end of which it was quenched by rapid addition of 0.5 mL of methanol, allowed to warm slowly and left for one more hour at room temperature. The workup and chromatography were carried out as described in Procedure A. With N-ethyl-N,N-diisopropylamine, (R)-5-trifluoromethyl-2-phenyl-2,3-dihydroimidazo[1,2-a]pyridine in toluene, Time= 8.25h, T= 0 °C , Resolution of racemate, Product distribution / selectivity Patent; Birman, Vladimir; US2005/256150; (2005); (A1) English View in Reaxys B.3.2 :Procedure B: Variation of the solvent 1) The stock solution of the catalyst was prepared by dissolving 0.040 mmol of 2d (10.6 mg) and 1.5 mmol of N,N-diisopropylethylamine (262]L, 194 mg) in the reaction solvent in a 2 mL volumetric test tube and bringing the volume to the mark. 2) A one-dram vial was charged with 0.5 mmol of (O)-phenyl ethyl carbinol and 0.500 mL of the stock solution of 2d cooled in an ice bath. After 15 minutes, 0.375 mmol of propionic anhydride was added. The mixture was swirled and left in the ice bath for 8 hours, at the end of which it was quenched by rapid addition of 0.5 mL of methanol, allowed to warm slowly and left for one more hour at room temperature. The workup and chromatography were carried out as described in Procedure A. With N-ethyl-N,N-diisopropylamine, (R)-5-trifluoromethyl-2-phenyl-2,3-dihydroimidazo[1,2-a]pyridine in diethyl ether, Time= 8.25h, T= 0 °C , Resolution of racemate, Product distribution / selectivity Patent; Birman, Vladimir; US2005/256150; (2005); (A1) English View in Reaxys B.3.5 :Procedure B: Variation of the solvent 1) The stock solution of the catalyst was prepared by dissolving 0.040 mmol of 2d (10.6 mg) and 1.5 mmol of N,N-diisopropylethylamine (262]L, 194 mg) in the reaction solvent in a 2 mL volumetric test tube and bringing the volume to the mark. 2) A one-dram vial was charged with 0.5 mmol of (O)-phenyl ethyl carbinol and 0.500 mL of the stock solution of 2d cooled in an ice bath. After 15 minutes, 0.375 mmol of propionic anhydride was added. The mixture was swirled and left in the ice bath for 8 hours, at the end of which it was quenched by rapid addition of 0.5 mL of methanol, allowed to warm slowly and left for one more hour at room temperature. The workup and chromatography were carried out as described in Procedure A.

230/258

2018-07-03 17:29:03

With N-ethyl-N,N-diisopropylamine, (R)-5-trifluoromethyl-2-phenyl-2,3-dihydroimidazo[1,2-a]pyridine in tert-Amyl alcohol, Time= 8.25h, T= 0 °C , Resolution of racemate, Product distribution / selectivity Patent; Birman, Vladimir; US2005/256150; (2005); (A1) English View in Reaxys With 2-phenyl-3,4-dihydro-2H-benzo[4,5]thiazolo[3,2-a]pyrimidine, N-ethyl-N,N-diisopropylamine in tert-Amyl alcohol, toluene, Time= 10h, T= -40 °C , optical yield given as percent ee Birman, Vladimir B.; Li, Ximin; Organic Letters; vol. 10; nb. 6; (2008); p. 1115 - 1118 View in Reaxys With (2S,3R)-3-methyl-2-phenyl-3,4-dihydro-2H-benzo[4,5]thiazolo[3,2-a]pyrimidine, sodium sulfate, N-ethyl-N,N-diisopropylamine in toluene, Time= 11h, T= -40 °C , Resolution of racemate, optical yield given as percent ee, enantioselective reaction Zhang, Yuhua; Birman, Vladimir B.; Advanced Synthesis and Catalysis; vol. 351; nb. 14-15; (2009); p. 2525 - 2529 View in Reaxys H (v2)

H OH

Rx-ID: 28938098 View in Reaxys 100/176 Yield

Conditions & References

19 %

Stage 1: With (1S,4R)-(7,7-dimethyl-2-morpholin-4-yl-bicyclo[2.2.1]hept-1-yl)methanethiol in tetrahydrofuran, toluene, Time= 2h, T= 20 °C , Inert atmosphere Stage 2: in tetrahydrofuran, toluene, Time= 22h, T= 0 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Wu, Ping-Yu; Wu, Hsyueh-Liang; Shen, Ying-Ying; Uang, Biing-Jiun; Tetrahedron Asymmetry; vol. 20; nb. 16; (2009); p. 1837 - 1841 View in Reaxys

O B

H OH

Rx-ID: 29027390 View in Reaxys 101/176 Yield

Conditions & References With 2,6-di-tert-butyl-4-methyl-phenol, water, dihydrogen peroxide, sodium hydroxide in tetrahydrofuran, T= 0 - 20 °C , Inert atmosphere Bagutski, Viktor; Ros, Abel; Aggarwal, Varinder K.; Tetrahedron; vol. 65; nb. 48; (2009); p. 9956 - 9960 View in Reaxys

231/258

2018-07-03 17:29:03

O HO

O O

H HO

Rx-ID: 29677416 View in Reaxys 102/176 Yield

Conditions & References

41 %

With (R)-(-)-benzotetramisole, N-ethyl-N,N-diisopropylamine in dichloromethane, Time= 12h, T= 20 °C , optical yield given as percent ee, enantioselective reaction Shiina, Isamu; Nakata, Kenya; Sugimoto, Masuhiro; Onda, Yu-Suke; Iizumi, Takashi; Ono, Keisuke; Heterocycles; vol. 77; nb. 2; (2009); p. 801 - 810 View in Reaxys O

H HO

Rx-ID: 29677421 View in Reaxys 103/176 Yield

Conditions & References

30 %

O O HO

HO O O

232/258

2018-07-03 17:29:03

O O

H HO

Rx-ID: 29677422 View in Reaxys 104/176 Yield

Conditions & References With (R)-(-)-benzotetramisole, 2,2-dimethylpropanoic anhydride, N-ethyl-N,N-diisopropylamine in dichloromethane, Time= 12h, T= 20 °C , optical yield given as percent ee, enantioselective reaction Shiina, Isamu; Nakata, Kenya; Sugimoto, Masuhiro; Onda, Yu-Suke; Iizumi, Takashi; Ono, Keisuke; Heterocycles; vol. 77; nb. 2; (2009); p. 801 - 810 View in Reaxys

H HO

Rx-ID: 10278616 View in Reaxys 105/176 Yield

Conditions & References With 3 A molecular sieve, Humicola insolens ferulic acid esterase, Time= 72h, T= 45 °C Hatzakis, Nikos S.; Smonou, Ioulia; Bioorganic Chemistry; vol. 33; nb. 4; (2005); p. 325 - 337 View in Reaxys With M. esculenta enzyme preparation immobilized on alginate gel in diethyl ether, Time= 116h, T= 45 °C , Title compound not separated from byproducts. Machado, Luciana L.; Lemos, Telma L.G.; de Mattos, Marcos Carlos; de Oliveira, Maria da Conceicao F.; de Gonzalo, Gonzalo; Gotor-Fernandez, Vicente; Gotor, Vicente; Tetrahedron Asymmetry; vol. 19; nb. 12; (2008); p. 1418 - 1423 View in Reaxys

HO H

Mg Cl

H O

Rx-ID: 26044771 View in Reaxys 106/176 Yield 31 %

Conditions & References With titanium(IV) isopropylate in diethyl ether, dichloromethane, Time= 1h, T= 0 °C , Title compound not separated from byproducts. Muramatsu, Yusuke; Harada, Toshiro; Angewandte Chemie - International Edition; vol. 47; nb. 6; (2008); p. 1088 - 1090 View in Reaxys

233/258

2018-07-03 17:29:03

H B

O OH

Rx-ID: 28314398 View in Reaxys 107/176 Yield

Conditions & References

93 %

With titanium(IV) isopropylate, (R)-3-(3,5-diphenylphenyl)-H8-BINOL in tetrahydrofuran, Time= 2h, T= 66 °C , Inert atmosphere, optical yield given as percent ee, enantioselective reaction Ukon, Takahiro; Harada, Toshiro; European Journal of Organic Chemistry; nb. 26; (2008); p. 4405 - 4407 View in Reaxys

Si O

H HO

Rx-ID: 28401911 View in Reaxys 108/176 Yield

Conditions & References With tetrabutyl ammonium fluoride in tetrahydrofuran, Time= 12h, Inert atmosphere, optical yield given as percent ee Clive, Derrick L. J.; Stoffman, Elia J. L.; Organic and Biomolecular Chemistry; vol. 6; nb. 10; (2008); p. 1831 - 1842 View in Reaxys

H HO

O OH

Rx-ID: 4995407 View in Reaxys 109/176 Yield

Conditions & References With Paecilomyces sp, biotransformation by diverse microorganisms, conversion percent, enantiomeric excess Adam, Waldemar; Boss, Barbara; Harmsen, Dag; Lukacs, Zoltan; Saha-Moeller, Chantu R.; Schreier, Peter; Journal of Organic Chemistry; vol. 63; nb. 22; (1998); p. 7598 - 7599 View in Reaxys With (Rp)-xylyl-PHANEPHOS in chloroform-d1, T= -67 - 25 °C , Title compound not separated from byproducts. Driver, Tom G.; Harris, Jason R.; Woerpel; Journal of the American Chemical Society; vol. 129; nb. 13; (2007); p. 3836 3837 View in Reaxys

234/258

2018-07-03 17:29:03

-1

B F

S+

(v4)

H H

F F

H O

Rx-ID: 9775482 View in Reaxys 110/176 Yield

Conditions & References

98 %

Stage 1: With lithium hexamethyldisilazane in tetrahydrofuran, dichloromethane, Time= 1h, T= -78 °C Stage 2: in tetrahydrofuran, dichloromethane, T= -100 - 0 °C Stage 3: With sodium hydroxide, dihydrogen peroxide in tetrahydrofuran, dichloromethane, T= 0 - 20 °C , Further stages. Fang, Guang Y.; Wallner, Olov A.; Di Blasio, Nadia; Ginesta, Xavier; Harvey, Jeremy N.; Aggarwal, Varinder K.; Journal of the American Chemical Society; vol. 129; nb. 47; (2007); p. 14632 - 14639 View in Reaxys

73 %

Stage 1: With lithium hexamethyldisilazane in tetrahydrofuran, 1,4-dioxane, Time= 5h, T= 5 °C Stage 2: With sodium hydroxide, dihydrogen peroxide Aggarwal, Varinder K.; Guang, Yu Fang; Schmidt, Andreas T.; Journal of the American Chemical Society; vol. 127; nb. 6; (2005); p. 1642 - 1643 View in Reaxys O

H HO

Rx-ID: 11272681 View in Reaxys 111/176 Yield

O HO

O O

235/258

2018-07-03 17:29:03

O H HO

Rx-ID: 11272684 View in Reaxys 112/176 Yield

H HO

Rx-ID: 11272685 View in Reaxys 113/176 Yield

H OH

Rx-ID: 7245876 View in Reaxys 114/176 Yield 95 - 98 %

Conditions & References 3; 4 Product distribution / selectivity Patent; UNIVERSITY OF NOTTINGHAM; WO2006/79819; (2006); (A2) English View in Reaxys Bruer,H.-J.; Haller,R.; Tetrahedron Letters; (1972); p. 5227 - 5230 View in Reaxys Yamamoto,K. et al.; Journal of Organometallic Chemistry; vol. 46; (1972); p. C65 - C67 View in Reaxys Hayashi et al.; Tetrahedron Letters; (1976); p. 4351 View in Reaxys 4 : Resolution of racemic alcohols Cleaving of the protective group is achieved using methanolysis following the general procedure given in example (4b).

236/258

2018-07-03 17:29:03

(R)-1-phenylpropanol (II: Z=O, R'=phenyl, R"=H, R'"==ethyl): Out of 551 mg (R)-O-MBF-1-phenylpropanol (column chromatography (eluent: petrolether/ether=5:1, then ether) 199 mg (83percent) (R)-1-phenylpropanol are obtained as colourless oil. [η]D 20 =+41,7° (c=2,3 in n-hexane). Patent; Noe; Christian; US4497960; (1985); (A) English View in Reaxys

SiH O

H OH

Rx-ID: 10087486 View in Reaxys 115/176 Yield

Conditions & References With hydrogenchloride in tetrahydrofuran, T= 20 °C Imamoto, Tsuneo; Itoh, Takuma; Yamanoi, Yoshinori; Narui, Rintaro; Yoshida, Kazuhiro; Tetrahedron Asymmetry; vol. 17; nb. 4; (2006); p. 560 - 565 View in Reaxys

H HO

Rx-ID: 10425252 View in Reaxys 116/176 Yield

Conditions & References With benzo[1,3,2]dioxaborole, chiral boron-bis(oxazoline) derivative in dichloromethane, Time= 48h, T= 25 °C Bandini, Marco; Bottoni, Andrea; Cozzi, Pier Giorgio; Miscione, Gian Pietro; Monari, Magda; Pierciaccante, Rossana; Umani-Ronchi, Achille; European Journal of Organic Chemistry; nb. 20; (2006); p. 4596 - 4608 View in Reaxys HO

H OH

Rx-ID: 10505966 View in Reaxys 117/176 Yield

Conditions & References With polyoxyethylene (10) cetyl ether, n-octyl η-D-glucopyranoside, subtilisin Carlsberg, sodium carbonate in tetrahydrofuran, Time= 17h, T= 20 °C , Title compound not separated from byproducts

237/258

2018-07-03 17:29:03

Boren, Linnea; Martin-Matute, Belen; Xu, Yongmei; Cordova, Armando; Baeckvall, Jan-E.; Chemistry - A European Journal; vol. 12; nb. 1; (2006); p. 225 - 232 View in Reaxys

bis<chloro(η3-1,3-diphenylallyl)palladium>

H OH

Rx-ID: 12657988 View in Reaxys 118/176 Yield

Conditions & References Reaction Steps: 2 1: chiral t-butyl(methyl)phosphine-based rhodium complex / tetrahydrofuran / 30 h / -20 °C 2: HCl / tetrahydrofuran / 20 °C With hydrogenchloride, chiral t-butyl(methyl)phosphine-based rhodium in tetrahydrofuran Imamoto, Tsuneo; Itoh, Takuma; Yamanoi, Yoshinori; Narui, Rintaro; Yoshida, Kazuhiro; Tetrahedron Asymmetry; vol. 17; nb. 4; (2006); p. 560 - 565 View in Reaxys Reaction Steps: 2 1: AgBF4 / (S)-[RhBr(nbd)(oxazolinyl-carbene)] / CH2Cl2 / 10 h / -60 °C 2: K2CO3 / methanol / 4 h / 20 °C With silver tetrafluoroborate, potassium carbonate, (S)-[RhBr(nbd)(oxazolinyl-carbene)] in methanol, dichloromethane Cesar, Vincent; Beliemin-Laponnaz, Stephane; Wadepohl, Hubert; Gade, Lutz H.; Chemistry - A European Journal; vol. 11; nb. 9; (2005); p. 2862 - 2873 View in Reaxys Reaction Steps: 2 1: [Rh(cod)Cl]2; asymmetric tetraphenyl-tetraoxa-phosphazulene derivative / toluene / 240 h / 0 °C 2: 1 percent p-TsOH / methanol With toluene-4-sulfonic acid, chloro(1,5-cyclooctadiene)rhodium(I) dimer, asymmetric tetraphenyl-tetraoxa-phosphazulene derivative in methanol, toluene, 1: enantioselective hydrosilylation / 2: Hydrolysis Heldmann, Dieter K.; Seebach, Dieter; Helvetica Chimica Acta; vol. 82; nb. 7; (1999); p. 1096 - 1110 View in Reaxys

SiH O

H HO

Rx-ID: 4472526 View in Reaxys 119/176 Yield

Conditions & References With hydrogenchloride, Yield given. Yields of byproduct given. Title compound not separated from byproducts Nishibayashi, Yoshiaki; Segawa, Kyohei; Takada, Hiroya; Ohe, Kouichi; Uemura, Sakae; Chemical Communications; nb. 7; (1996); p. 847 - 848 View in Reaxys With toluene-4-sulfonic acid in methanol, Hydrolysis, Title compound not separated from byproducts Heldmann, Dieter K.; Seebach, Dieter; Helvetica Chimica Acta; vol. 82; nb. 7; (1999); p. 1096 - 1110 View in Reaxys With potassium carbonate in methanol, Time= 4h, T= 20 °C , Title compound not separated from byproducts

238/258

2018-07-03 17:29:03

Cesar, Vincent; Beliemin-Laponnaz, Stephane; Wadepohl, Hubert; Gade, Lutz H.; Chemistry - A European Journal; vol. 11; nb. 9; (2005); p. 2862 - 2873 View in Reaxys

H O

Rx-ID: 9793817 View in Reaxys 120/176 Yield

Conditions & References Stage 1: With titanium(IV) isopropylate, L-3-phenyllactic acid in tetrahydrofuran, toluene, Time= 4h, T= 18 °C Stage 2: in tetrahydrofuran, toluene, Time= 4h, T= 18 °C , Title compound not separated from byproducts Bauer, Tomasz; Gajewiak, Joanna; Tetrahedron Asymmetry; vol. 16; nb. 4; (2005); p. 851 - 855 View in Reaxys HO

H HO

Rx-ID: 9873547 View in Reaxys 121/176 Yield

Conditions & References

84 %

With [(C4Ph4COHOCC4Ph4)(μ-H)][(CO)4Ru2], Novozym(R) 435, 2,4-dimethylpentan-3-one in toluene, Time= 40h, T= 70 °C , p= 142.511Torr Verzijl, Gerard K.M.; De Vries, Johannes G.; Broxterman, Quirinus B.; Tetrahedron Asymmetry; vol. 16; nb. 9; (2005); p. 1603 - 1610 View in Reaxys O O

Rx-ID: 9875473 View in Reaxys 122/176

239/258

2018-07-03 17:29:03

Yield

Conditions & References With 1,3-bis-[(R)-1-(1-naphthyl)ethyl]-4,5-dihydro-3H-imidazolium tetrafluoroborate, potassium tert-butylate in tetrahydrofuran, Time= 6.5h, T= -78 - -20 °C , Further byproducts given. Title compound not separated from byproducts Kano, Taichi; Sasaki, Kouji; Maruoka, Keiji; Organic Letters; vol. 7; nb. 7; (2005); p. 1347 - 1349 View in Reaxys

(1R,2R)-O-Merrifield bound N-(2-hydroxy-1-methyl-2-phenyl-ethyl)-N-methyl-2'-phenylacetamide

H OH

Rx-ID: 13209939 View in Reaxys 123/176 Yield

Conditions & References Reaction Steps: 2 1.1: 100 percent / AgBF4 / CH2Cl2 / 48 h / 20 °C 2.1: LiHMDS / tetrahydrofuran; dioxane / 5 h / 5 °C 2.2: 73 percent / aq. NaOH; H2O2 With silver tetrafluoroborate, lithium hexamethyldisilazane in tetrahydrofuran, 1,4-dioxane, dichloromethane Aggarwal, Varinder K.; Guang, Yu Fang; Schmidt, Andreas T.; Journal of the American Chemical Society; vol. 127; nb. 6; (2005); p. 1642 - 1643 View in Reaxys

H HO

Rx-ID: 23655071 View in Reaxys 124/176 Yield

Conditions & References A.1.3 :To a solution of 0.25 mmol of phenylethylcarbinol (34 L, 34 mg) and 0.050 mmol of the catalyst (2a-d) in 0.250 mL CDCl3 was added 0.25 mmol of acetic anhydride (24 L, 26 mg). The mixture was swirled, left at room temperature for 1 hour, quenched by rapid addition of 0.25 mL of methanol, and left for one more hour. The reaction mixture was diluted with CH2Cl2, washed twice with 1 M HCl, then twice with saturated aqueous NaHCO3, and dried over Na2SO4. The solution was concentrated on a rotary evaporator at room temperature and chromatographed (5-20percent Et2O in hexanes) to separate the ester from the unreacted alcohol. With (R)-5-nitro-2-phenyl-2,3-dihydroimidazo[1,2-a]pyridine in chloroform-d1, Time= 1h, T= 20 °C , Resolution of racemate, Product distribution / selectivity Patent; Birman, Vladimir; US2005/256150; (2005); (A1) English View in Reaxys A.1.6; C.4.2 :To a solution of 0.25 mmol of phenylethylcarbinol (34 L, 34 mg) and 0.050 mmol of the catalyst (2a-d) in 0.250 mL CDCl3 was added 0.25 mmol of acetic anhydride (24 L, 26 mg). The mixture was swirled, left at room temperature for 1 hour, quenched by rapid addition of 0.25 mL of methanol, and left for one more hour. The reaction mixture was diluted with CH2Cl2, washed twice with 1 M HCl, then twice with saturated aqueous NaHCO3, and dried over Na2SO4. The solution was concentrated on a rotary evaporator at room temperature and chromatographed (5-20percent Et2O in hexanes) to separate the ester from the unreacted alcohol.; The reaction time is expressed in hours and is shown under t(h). Entries 14 in Table 1 were obtained using 20 mol percent of the catalyst in deuterated chloroform CDCl3 at room temperature for 1 hour, and entries 5-14 were obtained using 2 mol percent of the catalyst at 0° C. in the presence of N,N-diisopropylethylamine in chloroform CHCl3 for the specified period of time. The esters produced and the unreacted alcohols resulting from kinetic resolution experiments were analyzed by chiral HPLC to determine their enantiomeric excesses (see below). HPLC analyses were performed on a Breeze LC system (Waters Corporation) and CHIRALCEL OD-H analytical column (4.6x250 mm, Chiral Technologies, Inc.) using isopropanol-hexanes mobile phase at a flow rate of 1 mL/min and UV detection at 254 nm. Specific optical rotations were measured using a Perkin-Elmer 241 polarimeter. The absolute chirality of the esters and alcohols obtained by kinetic resolution was deter-

240/258

2018-07-03 17:29:03

mined by the sign of the optical rotation of the unreacted alcohol.; Procedure C. Variation of the substrate and the acylating agent in the CF3PIP-catalyzed kinetic resolutions. 1) The stock solution of the catalyst was prepared by dissolving 0.100 mmol of 2d (26.4 mg) and 3.75 mmol of N,N-diisopropylethylamine (6540L, 485 mg) in CHCl3 in a 5 mL volumetric flask and bringing the volume to the mark. 2) A one-dram vial was charged with 0.5 mmol of the racemic secondary alcohol and 0.500 mL of the stock solution of 2d, and cooled in an ice bath. After 15 minutes, 0.375 mmol of the anhydride was added. The mixture was swirled and left in the ice bath for a specified period of time, at the end of which it was quenched by rapid addition of 0.5 mL of methanol, allowed to warm slowly and left for one more hour at room temperature. The workup and chromatography were carried out as described in Procedure A. With N-ethyl-N,N-diisopropylamine, (R)-5-trifluoromethyl-2-phenyl-2,3-dihydroimidazo[1,2-a]pyridine in chloroform, Time= 8 - 8.25h, T= 0 °C , Resolution of racemate, Product distribution / selectivity Patent; Birman, Vladimir; US2005/256150; (2005); (A1) English View in Reaxys

Rx-ID: 23674596 View in Reaxys 125/176 Yield

Conditions & References The enantiomeric excesses of the esters were determined, in most cases, by hydrolysis to the parent alcohols (2 mL of 2 M KOH in methanol, at room temperature until complete by TLC), which were analyzed as described above. With potassium hydroxide in methanol, T= 20 °C Patent; Birman, Vladimir; US2005/256150; (2005); (A1) English View in Reaxys

H HO

Rx-ID: 9599244 View in Reaxys 126/176 Yield

Conditions & References With diethylzinc, [2-((S)-4-tBu-4,5-H2-oxazol-2-yl)-1-(C(OH)Ph2)]-ferrocene in n-heptane, toluene, Time= 12h, T= 10 °C , Title compound not separated from byproducts. Rudolph, Jens; Schmidt, Frank; Bolm, Carsten; Advanced Synthesis and Catalysis; vol. 346; nb. 7; (2004); p. 867 - 872 View in Reaxys

H HO

Rx-ID: 9717265 View in Reaxys 127/176

241/258

2018-07-03 17:29:03

Yield

Conditions & References Stage 1: With (S)-2-methyl-quinazolinap rhodium, benzo[1,3,2]dioxaborole in tetrahydrofuran, Time= 2h, T= 0 °C Stage 2: With sodium hydroxide, dihydrogen peroxide in tetrahydrofuran, ethanol, T= 0 - 20 °C , Title compound not separated from byproducts Connolly, David J.; Lacey, Patrick M.; McCarthy, Mary; Saunders, Cormac P.; Carroll, Anne-Marie; Goddard, Richard; Guiry, Patrick J.; Journal of Organic Chemistry; vol. 69; nb. 20; (2004); p. 6572 - 6589 View in Reaxys Stage 1: With (R)-2-tert-butyl-quinazolinap rhodium, benzo[1,3,2]dioxaborole in tetrahydrofuran, Time= 4h, T= 0 °C Stage 2: With sodium hydroxide, dihydrogen peroxide in tetrahydrofuran, ethanol, T= 0 - 20 °C , Title compound not separated from byproducts Connolly, David J.; Lacey, Patrick M.; McCarthy, Mary; Saunders, Cormac P.; Carroll, Anne-Marie; Goddard, Richard; Guiry, Patrick J.; Journal of Organic Chemistry; vol. 69; nb. 20; (2004); p. 6572 - 6589 View in Reaxys

H HO

Rx-ID: 9721780 View in Reaxys 128/176 Yield

Conditions & References Stage 1: With (R)-2-tert-butyl-quinazolinap rhodium, benzo[1,3,2]dioxaborole in tetrahydrofuran, Time= 2h, T= 20 °C Stage 2: With sodium hydroxide, dihydrogen peroxide in tetrahydrofuran, ethanol, T= 0 - 20 °C , Title compound not separated from byproducts Connolly, David J.; Lacey, Patrick M.; McCarthy, Mary; Saunders, Cormac P.; Carroll, Anne-Marie; Goddard, Richard; Guiry, Patrick J.; Journal of Organic Chemistry; vol. 69; nb. 20; (2004); p. 6572 - 6589 View in Reaxys

H OH

Rx-ID: 13555896 View in Reaxys 129/176 Yield

Conditions & References Reaction Steps: 2 1: trichlorosilane; [(R)-1,1'-spirobiindane-7,7'-dioxy][((R)-PhMeCH)2N]phosphane / [Pd(η3-allyl)Cl]2 / 36 h / 15 - 20 °C 2: H2O2; KF; KHCO3 / methanol; tetrahydrofuran With potassium fluoride, (11aR)-(+)-10,11,12,13-tetrahydrodiindeno-[7,1-de:1',7'-fg][1,3,2]dioxaphosphocin-5-bis[(R)-1-phenylethyl]amine, trichlorosilane, dihydrogen peroxide, potassium hydrogencarbonate, bis(η3-allyl-μ-chloropalladium(II)) in tetrahydrofuran, methanol Guo, Xun-Xiang; Xie, Jian-Hua; Hou, Guo-Hua; Shi, Wen-Jian; Wang, Li-Xin; Zhou, Qi-Lin; Tetrahedron Asymmetry; vol. 15; nb. 14; (2004); p. 2231 - 2234 View in Reaxys Reaction Steps: 2 1.1: (SA,RC,RC)-BINOL=P-N-(1-ethylphenyl)2; allylpalladium chloride dimer / 0.33 h / 20 °C 1.2: 91 percent / trichlorosilane / 40 h / 20 °C 2.1: KF; KHCO3; aq. H2O2 / methanol; tetrahydrofuran / 16 h / 20 °C With potassium fluoride, dihydrogen peroxide, potassium hydrogencarbonate, bis(η3-allyl-μ-chloropalladium(II)), (SA,RC,RC)BINOL=P-N-(1-ethylphenyl)2 in tetrahydrofuran, methanol, 2.1: Tamao oxidation

242/258

2018-07-03 17:29:03

Jensen, Jakob F.; Svendsen, Bo Y.; La Cour, Thomas V.; Pedersen, Henriette L.; Johannsen, Mogens; Journal of the American Chemical Society; vol. 124; nb. 17; (2002); p. 4558 - 4559 View in Reaxys

Et2Zn

Rx-ID: 7245882 View in Reaxys 130/176 Yield 100 %

Conditions & References With (-)-erythro-PMPM in hexane, T= 0 °C Soai, Kenso; Ookawa, Atsuhiro; Ogawa, Kazuo; Kaba, Tatsuya; Journal of the Chemical Society, Chemical Communications; nb. 6; (1987); p. 467 - 468 View in Reaxys

98 %

With (+)-DPMPM in hexane, Time= 4h, T= 0 °C Soai, Kenso; Ookawa, Atsuhiro; Ogawa, Kazuo; Kaba, Tatsuya; Journal of the Chemical Society, Chemical Communications; nb. 6; (1987); p. 467 - 468 View in Reaxys With hydrogenchloride, 1,1-diethyl-3-(3'-indolyl)-(2S)-(N-methyl-N-3'',3''-dimethylbutylamino)-1-propanol, 1.) PhMe, RT, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Dai; Zhu; Hao; Tetrahedron Asymmetry; vol. 6; nb. 8; (1995); p. 1857 - 1860 View in Reaxys With η-amino amid derived from L-phenylanaline (R'=Ph), nickel diacetate in methanol, toluene, Time= 24h, T= 20 °C Burguete, M. Isabel; Collado, Manuel; Escorihuela, Jorge; Galindo, Francisco; Garcia-Verdugo, Eduardo; Luis, Santiago V.; Vicent, Maria J.; Tetrahedron Letters; vol. 44; nb. 36; (2003); p. 6891 - 6894 View in Reaxys With (RFc,RS)-2-(p-Tolylamino)-1-tert-butylsulfinylferrocene in hexane, toluene, T= 20 °C , Product distribution, Further Variations: Reagents Priego; Garcia Mancheno; Cabrera; Carretero; Chemical Communications; nb. 19; (2001); p. 2026 - 2027 View in Reaxys

diethylzinc

Rx-ID: 8988737 View in Reaxys 131/176 Yield

Conditions & References With ephedrine in toluene, Time= 24h, T= 20 °C Hu, Qiao-Sheng; Sun, Chaode; Monaghan, Colleen E; Tetrahedron Letters; vol. 42; nb. 44; (2001); p. 7725 - 7728 View in Reaxys With (R)-2-[(1-ferrocenylethylimino)methyl]phenol in toluene, T= 0 °C , Product distribution, Further Variations: Reagents, Solvents, Temperatures

243/258

2018-07-03 17:29:03

Kim, Tae-Jeong; Lee, Hee-Yeol; Ryu, Eun-Sook; Park, Dong-Kyu; Cho, Chan Sik; Shim, Sang Chul; Jeong, Jong Hwa; Journal of Organometalic Chemistry; vol. 649; nb. 2; (2002); p. 258 - 267 View in Reaxys With titanium(IV) isopropylate, chiral osmaimidazolidine ligand in toluene, T= -30 °C , Title compound not separated from byproducts Muniz, Kilian; Tetrahedron Letters; vol. 44; nb. 17; (2003); p. 3547 - 3549 View in Reaxys With 1-methyl-cis-decahydro-quinolin-7-ol in tetrahydrofuran, toluene, Time= 8h, T= 20 °C , Product distribution, Further Variations: Reaction partners, Reagents, Solvents Panda, Manoranjan; Phuan, Puay-Wah; Kozlowski, Marisa C.; Journal of Organic Chemistry; vol. 68; nb. 2; (2003); p. 564 - 571 View in Reaxys With (R)-2-(pyrrolidin-1-yl-methyl)-2'-hydroxy-1,1'-binaphthyl in hexane, toluene, Time= 24h, T= 20 °C , Title compound not separated from byproducts. Ko, Dong-Hyun; Kim, Kyoung Hoon; Ha, Deok-Chan; Organic Letters; vol. 4; nb. 21; (2002); p. 3759 - 3762 View in Reaxys

H O

Rx-ID: 2681327 View in Reaxys 132/176 Yield

Conditions & References With n-butyllithium, (2S,2'S)-2-hydroxymethyl-1-<(1-methylpyrrolidine-2-yl)methyl>pyrrolidine in toluene, Time= 1h, T= -110 °C , investigation of the asymmetric addition of dialkylmagnesium to an aldehyde in toluene in presence (2S,2S')-2-hydroxymethyl-1-<(1-methylpyrrolidine-2-yl)methyl>pyrrolidine, Product distribution, Mechanism Mukaiyama, Teruaki; Tetrahedron; vol. 37; nb. 23; (1981); p. 4111 - 4119 View in Reaxys With (5aS,10aS)-(-)-Octahydro-5H,10H-dipyrrolo<1,2-a:1',2'-d>pyrazin in diethyl ether, pentane, Time= 5h, T= -90 °C , Heating, other carbonyl compounds, other solvents, other temperatures, Product distribution, Mechanism Zadel, Guido; Breitmaier, Eberhard; Chemische Berichte; vol. 127; nb. 7; (1994); p. 1323 - 1326 View in Reaxys With n-butyllithium, (2S,2'S)-2-hydroxymethyl-1-<(1-methylpyrrolidine-2-yl)methyl>pyrrolidine in toluene, Time= 1h, T= -110 °C , Yield given. Yields of byproduct given Mukaiyama, Teruaki; Tetrahedron; vol. 37; nb. 23; (1981); p. 4111 - 4119 View in Reaxys With (5aS,10aS)-(-)-Octahydro-5H,10H-dipyrrolo<1,2-a:1',2'-d>pyrazin in diethyl ether, pentane, Time= 5h, T= -90 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Zadel, Guido; Breitmaier, Eberhard; Chemische Berichte; vol. 127; nb. 7; (1994); p. 1323 - 1326 View in Reaxys Stage 1: With methyl-((R)-1-phenyl-2-piperidin-1-yl-ethyl)-amine in tetrahydrofuran, diethyl ether, T= -78 - 20 °C Stage 2: in tetrahydrofuran, diethyl ether, T= -78 - 20 °C , Further stages. Title compound not separated from byproducts. Yong, Kelvin H.; Taylor, Nicholas J.; Chong, J. Michael; Organic Letters; vol. 4; nb. 21; (2002); p. 3553 - 3556 View in Reaxys

244/258

2018-07-03 17:29:03

diethylzinc

O OH

Rx-ID: 9117006 View in Reaxys 133/176 Yield

Conditions & References

89 %

With titanium(IV) isopropylate, (R,R)-1,1'-bis(1-ferrocenylethanol) in hexane, toluene, Time= 48h, T= 20 °C Kim, Tae-Jeong; Lee, Hee-Yeol; Ryu, Eun-Sook; Park, Dong-Kyu; Cho, Chan Sik; Shim, Sang Chul; Jeong, Jong Hwa; Journal of Organometalic Chemistry; vol. 649; nb. 2; (2002); p. 258 - 267 View in Reaxys

N HO

H HO

Rx-ID: 9130399 View in Reaxys 134/176 Yield

Conditions & References With aluminium trichloride in hexane, toluene, Time= 17h, T= -5 °C , Title compound not separated from byproducts Kashima, Choji; Mizuhara, Saori; Miwa, Yohei; Yokoyama, Yukihiro; Tetrahedron Asymmetry; vol. 13; nb. 16; (2002); p. 1713 - 1719 View in Reaxys

H (v2)

H O

Rx-ID: 9140253 View in Reaxys 135/176 Yield

Conditions & References With chiral MeO-PEG-supported ferrocenyl oxazoline, diethylzinc in toluene, T= 10 °C Bolm, Carsten; Hermanns, Nina; Classen, Arno; Muiz, Kilian; Bioorganic and Medicinal Chemistry Letters; vol. 12; nb. 14; (2002); p. 1795 - 1798 View in Reaxys

245/258

2018-07-03 17:29:03

H HO

Rx-ID: 9147629 View in Reaxys 136/176 Yield

Conditions & References

40 %

With tetrabutylammonium tetrafluoroborate, (1R,2S)-(-)-N,N-dimethylephedrinium tetrafluoroborate in water, N,N-dimethylformamide, Electrolysis Yadav, Ashok K.; Singh, Arpita; Bulletin of the Chemical Society of Japan; vol. 75; nb. 3; (2002); p. 587 - 588 View in Reaxys

O (v2)

HO O N

H HO

Rx-ID: 9256542 View in Reaxys 137/176 Yield

Conditions & References With chiral bis(oxazoline) compound, Title compound not separated from byproducts Klein, Guenter; Pandiaraju, Subramaniam; Reiser, Oliver; Tetrahedron Letters; vol. 43; nb. 42; (2002); p. 7503 - 7506 View in Reaxys

H HO

Rx-ID: 9319917 View in Reaxys 138/176 Yield

Conditions & References With tertiary amine-based nucleophilic catalyst in tert-Amyl alcohol, Time= 16h, T= 0 Â°C Jeong, Kyu-Sung; Kim, Soong-Hyun; Park, Hyun-Jin; Chang, Kyoung-Jin; Kwan, Soo Kim; Chemistry Letters; nb. 11; (2002); p. 1114 - 1115 View in Reaxys

Copyright ÂŠ 2018 Elsevier Life Sciences IP Limited except certain content provided by third parties. Reaxys is a trademark of Elsevier Life Sciences IP Limited.

246/258

2018-07-03 17:29:03

O HO O

O HO

Rx-ID: 8958880 View in Reaxys 139/176 Yield

Conditions & References Stage 1: With sodium tetrahydroborate in water, Time= 2h, T= 20 Â°C Stage 2: in water, Time= 3h Miyamoto; Yasaka; Takaoka; Tanaka; Toda; Enantiomer; vol. 6; nb. 1; (2001); p. 51 - 55 View in Reaxys

H (v2)

H O

Rx-ID: 10306736 View in Reaxys 140/176 Yield

Conditions & References With (R)-aromatic alcohol dehydrogenase (Lactobacillus kefir), (S)-aromatic alcohol dehydrogenase (Thermoanaerobium sp.), (S)-(-)-2,2-dimethyl-5,5-diphenyl-4-isopropyl-1,3-oxazolidine in toluene, Product distribution, Enzyme kinetics, Kinetics, Further Variations: Solvents, Reagents, Catalysts Abato; Seto; Journal of the American Chemical Society; vol. 123; nb. 37; (2001); p. 9206 - 9207 View in Reaxys With (R)-aromatic alcohol dehydrogenase (Lactobacillus kefir), (S)-aromatic alcohol dehydrogenase (Thermoanaerobium sp.), (R)-4-isopropyl-2,2-dimethyl-oxazolidine in toluene, Product distribution, Enzyme kinetics, Kinetics, Further Variations: Solvents, Reagents, Catalysts Abato; Seto; Journal of the American Chemical Society; vol. 123; nb. 37; (2001); p. 9206 - 9207 View in Reaxys

Copyright ÂŠ 2018 Elsevier Life Sciences IP Limited except certain content provided by third parties. Reaxys is a trademark of Elsevier Life Sciences IP Limited.

247/258

2018-07-03 17:29:03

O HO

O O

H HO

Rx-ID: 5322067 View in Reaxys 141/176 Yield

Conditions & References With Lipase PS in di-isopropyl ether, Time= 25h, T= 30 °C , Enzymatic reaction, Esterification Kita, Yasuyuki; Takebe, Yasushi; Murata, Kenji; Naka, Tadaatsu; Akai, Shuji; Journal of Organic Chemistry; vol. 65; nb. 1; (2000); p. 83 - 88 View in Reaxys

(v2)

H HO

Rx-ID: 5360739 View in Reaxys 142/176 Yield

Conditions & References With (1R,2R,4S)-2-Me2NCH2C6H4-1,3,3-Me3-bicyclo[2.2.1]heptan-2-ol in hexane, Time= 24h, T= 6 °C , Condensation, Product distribution, Further Variations: Reagents, Temperatures Goldfuss, Bernd; Steigelmann, Melanie; Khan, Saeed I.; Houk; Journal of Organic Chemistry; vol. 65; nb. 1; (2000); p. 77 82 View in Reaxys

H HO

Rx-ID: 8618423 View in Reaxys 143/176 Yield

248/258

2018-07-03 17:29:03

H O

Rx-ID: 8700420 View in Reaxys 144/176 Yield

Conditions & References

96 %

With sodium tetrahydroborate, chloro-trimethyl-silane, (S)-diphenylprolinol in tetrahydrofuran, Time= 1h, T= 25 - 70 °C Jiang, Biao; Feng, Yan; Zheng, Jian; Tetrahedron Letters; vol. 41; nb. 52; (2000); p. 10281 - 10283 View in Reaxys

(v2)

H HO

Rx-ID: 5153895 View in Reaxys 145/176 Yield

Conditions & References With (R)-C56H70O6 in toluene, Time= 20h, T= 0 °C , Yield given, Yields of byproduct given. Title compound not separated from byproducts Huang, Wei-Sheng; Pu, Lin; Journal of Organic Chemistry; vol. 64; nb. 12; (1999); p. 4222 - 4223 View in Reaxys Stage 1: With (R)-3,3'-bis(2'',4''-dihexyloxyphenyl)-1,1'-binaphthol, diethylzinc in toluene, Time= 0.25h, T= 20 °C , Substitution Stage 2: in toluene, Time= 20h, T= 0 °C , Addition, Title compound not separated from byproducts Huang, Wei-Sheng; Hu, Qiao-Sheng; Pu, Lin; Journal of Organic Chemistry; vol. 64; nb. 21; (1999); p. 7940 - 7956 View in Reaxys

H HO

O OH

Rx-ID: 5200370 View in Reaxys 146/176 Yield

Conditions & References With Coprinus peroxidase (CiP), 2-methoxy-phenol in water, Time= 20h, T= 72 °C , phosphate buffer pH 7.0; enzyme-catalyzed kinetic resolution of chiral hydroperoxides in the presence and absence of guaiacol; selectivity; enantiomeric excess; CiPcatalyzed disproportionation; radical formation; mechanism; CiP-catalyzed sulfoxidation, Product distribution Adam, Waldemar; Mock-Knoblauch, Cordula; Saha-Moeller, Chantu R.; Journal of Organic Chemistry; vol. 64; nb. 13; (1999); p. 4834 - 4839 View in Reaxys

249/258

2018-07-03 17:29:03

H HO

Rx-ID: 4677548 View in Reaxys 147/176 Yield

Conditions & References With phosphate buffer pH 6.0, 2-methoxy-phenol, horseradish peroxidase, Time= 1h, Ambient temperature, Title compound not separated from byproducts Adam, Waldemar; Korb, Marion N.; Tetrahedron Asymmetry; vol. 8; nb. 7; (1997); p. 1131 - 1142 View in Reaxys

O H

OH OH

Rx-ID: 4188537 View in Reaxys 148/176 Yield

Conditions & References in methanol, water, penicillin G acylase in pH 8 phosphate buffer, Rate constant Pohl; Waldmann; Tetrahedron Letters; vol. 36; nb. 17; (1995); p. 2963 - 2966 View in Reaxys

O H OH

Rx-ID: 4188538 View in Reaxys 149/176 Yield

Conditions & References in methanol, water, penicillin G acylase in pH 8 phosphate buffer Pohl; Waldmann; Tetrahedron Letters; vol. 36; nb. 17; (1995); p. 2963 - 2966 View in Reaxys

O OH

Rx-ID: 4352541 View in Reaxys 150/176 Yield

Conditions & References With N-methyl ephedrine disulfide, diethylzinc, multistep; other N-methyl ephedrine derivatives, Mechanism

Copyright ÂŠ 2018 Elsevier Life Sciences IP Limited except certain content provided by third parties. Reaxys is a trademark of Elsevier Life Sciences IP Limited.

250/258

2018-07-03 17:29:03

Fitzpatrick, Kevin; Hulst, Ron; Kellogg, Richard M.; Tetrahedron: Asymmetry; vol. 6; nb. 8; (1995); p. 1861 - 1864 View in Reaxys

H HO

Rx-ID: 4519980 View in Reaxys 151/176 Yield

Conditions & References With potassium phosphate buffer, 2-methoxy-phenol, horseradish peroxidase, Yield given. Yields of byproduct given Adam; Hoch; Lazarus; Saha-Moller; Schreier; Journal of the American Chemical Society; vol. 117; nb. 48; (1995); p. 11898 - 11901 View in Reaxys With potassium phosphate buffer, horseradish peroxidase, Rate constant Adam; Hoch; Lazarus; Saha-Moller; Schreier; Journal of the American Chemical Society; vol. 117; nb. 48; (1995); p. 11898 - 11901 View in Reaxys Yield given. Yields of byproduct given Adam; Hoch; Lazarus; Saha-Moller; Schreier; Journal of the American Chemical Society; vol. 117; nb. 48; (1995); p. 11898 - 11901 View in Reaxys

H HO

Rx-ID: 1730197 View in Reaxys 152/176 Yield

Conditions & References With lipase YS in di-isopropyl ether, Time= 200h, T= 30 Â°C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Naemura, Koichiro; Fukuda, Ritsuko; Konishi, Masayoshi; Hirose, Keiji; Tobe, Yoshito; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); nb. 10; (1994); p. 1253 - 1256 View in Reaxys

H HO

Rx-ID: 2015383 View in Reaxys 153/176

Copyright ÂŠ 2018 Elsevier Life Sciences IP Limited except certain content provided by third parties. Reaxys is a trademark of Elsevier Life Sciences IP Limited.

251/258

2018-07-03 17:29:03

Yield

Conditions & References With Isopropenyl acetate, lipase YS in di-isopropyl ether, Time= 200h, T= 30 °C , Yield given. Yields of byproduct given. Title compound not separated from byproducts Naemura, Koichiro; Fukuda, Ritsuko; Konishi, Masayoshi; Hirose, Keiji; Tobe, Yoshito; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); nb. 10; (1994); p. 1253 - 1256 View in Reaxys

H HO

Rx-ID: 2121097 View in Reaxys 154/176 Yield

Conditions & References in acetonitrile, T= 27 - 28 °C , 0.1 M aq. phosphate buffer (pH 8.0), penicillin G aminohydrolase (PGA), Yield given. Yields of byproduct given. Title compound not separated from byproducts Baldaro; D'Arrigo; Pedrocchi-Fantoni; Rosell; Tagliani; Terreni; Servi; Tetrahedron Asymmetry; vol. 4; nb. 5; (1993); p. 1031 - 1034 View in Reaxys

(v2)

H HO

Rx-ID: 3401056 View in Reaxys 155/176 Yield

Conditions & References With (4S,5S)-4-Hydroxymethyl-2-methyl-5-phenyl-4,5-dihydro-1,3-oxazole in hexane, T= 20 °C , other aromatic aldehydea and enantiomerically pure hydroxymethyl oxazolines, Product distribution Allen; Frost; Williams; Tetrahedron Asymmetry; vol. 4; nb. 4; (1993); p. 649 - 650 View in Reaxys

ring hydrogenation products (8.2percent)

H OH

Rx-ID: 18425452 View in Reaxys 156/176 Yield

Conditions & References Reaction Steps: 2 1: HSiCl3, <PdCl(η-C3H5)>2, (R)-2-methoxy-2'-diphenylphosphino-1,1'-binaphthyl / toluene / 48 h / 40 °C 2: KF, KHCO3, 30percent aq. H2O2 / tetrahydrofuran; methanol / 10 h / Ambient temperature With (R)-(+)-2-(Diphenylphosphino)-2η-methoxy-1,1η-binaphthyl, potassium fluoride, bis(η3-allyl-μ-chloropalladium(II)), trichlorosilane, dihydrogen peroxide, potassium hydrogencarbonate in tetrahydrofuran, methanol, toluene Uozumi, Yasuhiro; Kitayama, Kenji; Hayashi, Tamio; Tetrahedron: Asymmetry; vol. 4; nb. 12; (1993); p. 2419 - 2422 View in Reaxys

252/258

2018-07-03 17:29:03

Rx-ID: 1990768 View in Reaxys 157/176 Yield 40 %

Conditions & References With phosphate buffer, lipase, T= 20 °C Laumen, Kurt; Schneider, Manfred P.; Journal of the Chemical Society, Chemical Communications; (1988); p. 598 - 600 View in Reaxys Basavaiah; Raju; Synthetic Communications; vol. 21; nb. 18-19; (1991); p. 1859 - 1863 View in Reaxys With sodium hydroxide, dm-3 phosphate buffer, T= 25 °C , lipoprotein lipase from Pseudomonas aeruginosa (LPL Amano 1), pH 6.9-7.0 Kim, Mahn-Joo; Cho, Hangjin; Journal of the Chemical Society, Chemical Communications; nb. 19; (1992); p. 1411 - 1413 View in Reaxys

O O Si H HO

Rx-ID: 2797370 View in Reaxys 158/176 Yield

Conditions & References With potassium fluoride, dihydrogen peroxide, potassium hydrogencarbonate, 1) THF, MeOH, 2) THF, MeOH, 60 deg C, 15 h, Yield given. Multistep reaction Buynak, John D.; Strickland, J. Byron; Lamb, Grady W.; Khasnis, Dipti; Modi, Seema; et al.; Journal of Organic Chemistry; vol. 56; nb. 25; (1991); p. 7076 - 7083 View in Reaxys

Si H

Rx-ID: 20949785 View in Reaxys 159/176 Yield

Conditions & References Reaction Steps: 2 1: 97 percent / pyridine, 4-(dimethylamino)pyridine / Ambient temperature 2: 1) KF, KHCO3, 2) 30percent H2O2 / 1) THF, MeOH, 2) THF, MeOH, 60 deg C, 15 h With pyridine, dmap, potassium fluoride, dihydrogen peroxide, potassium hydrogencarbonate Buynak, John D.; Strickland, J. Byron; Lamb, Grady W.; Khasnis, Dipti; Modi, Seema; et al.; Journal of Organic Chemistry; vol. 56; nb. 25; (1991); p. 7076 - 7083 View in Reaxys

253/258

2018-07-03 17:29:03

OH 2H

H 2H

Rx-ID: 2681701 View in Reaxys 160/176 Yield

Conditions & References With (+)-PhCD(OH)Et in benzene, Ambient temperature, other alkyllithium; multistep reaction, Product distribution Alberts, Albert H.; Wynberg, Hans; Journal of the American Chemical Society; vol. 111; nb. 18; (1989); p. 7265 - 7266 View in Reaxys

H HO

Rx-ID: 3799566 View in Reaxys 161/176 Yield

Conditions & References With (S)-4-phenyl-1,4-diaza<4.3.0>bicyclononane, diisobutylaluminium hydride, tin(ll) chloride in dichloromethane, Time= 0.166667h, T= -100 °C , Title compound not separated from byproducts Falorni, Massimo; Lardicci, Luciano; Piroddi, Anna Maria; Giacomelli, Giampaolo; Gazzetta Chimica Italiana; vol. 119; nb. 9; (1989); p. 511 - 512 View in Reaxys

H HO

Rx-ID: 2015384 View in Reaxys 162/176 Yield

Conditions & References Yield given. Yields of byproduct given. Title compound not separated from byproducts Bianchi, Daniele; Cesti, Pietro; Battistel, Ezio; Journal of Organic Chemistry; vol. 53; nb. 23; (1988); p. 5531 - 5534 View in Reaxys

O O

H OH

Rx-ID: 2825064 View in Reaxys 163/176 Yield

Conditions & References With sodium hydroxide, Time= 4h, T= 25 °C

254/258

2018-07-03 17:29:03

Bianchi, Daniele; Cesti, Pietro; Battistel, Ezio; Journal of Organic Chemistry; vol. 53; nb. 23; (1988); p. 5531 - 5534 View in Reaxys

O O

Rx-ID: 3964229 View in Reaxys 164/176 Yield

Conditions & References

46 %

With phosphate buffer, lipase, T= 20 °C Laumen, Kurt; Schneider, Manfred P.; Journal of the Chemical Society, Chemical Communications; (1988); p. 598 - 600 View in Reaxys

H (v2)

O OH

Rx-ID: 2681338 View in Reaxys 165/176 Yield

Conditions & References

68 % Chromat.

With tridentate lithium complex (6-Li salt) in toluene Corey, E. J.; Hannon, Francis J.; Tetrahedron Letters; vol. 28; nb. 44; (1987); p. 5233 - 5236 View in Reaxys H

(v2)

H HO

Rx-ID: 2681728 View in Reaxys 166/176 Yield

Conditions & References

10 %

With tridentate lithium salt (1-Li salt) in toluene, Time= 14h, T= 23 °C , Yield given. Yields of byproduct given Corey, E. J.; Hannon, Francis J.; Tetrahedron Letters; vol. 28; nb. 44; (1987); p. 5233 - 5236 View in Reaxys

OH H H OH

Rx-ID: 436086 View in Reaxys 167/176 Yield 95 %

Conditions & References With hydrogen, nickel, Time= 1.5h Davis, Franklin A.; Stringer, Orum D.; McCauley, John P., Jr.; Tetrahedron; vol. 41; nb. 21; (1985); p. 4747 - 4758 View in Reaxys With diethyl ether, nickel, Hydrogenation Duveen; Kenyon; Journal of the Chemical Society; (1939); p. 1697,1700

255/258

2018-07-03 17:29:03

View in Reaxys

Cl H OH

Rx-ID: 20668838 View in Reaxys 168/176 Yield

Conditions & References Reaction Steps: 3 1: 80 percent / NaBH4 / ethanol / 25 Â°C 2: 51 percent / pyridine / tetrahydrofuran; H2O / 6 h / Ambient temperature; asymmetric oxidation of using chiral oxaziridines to optically active allyl alcohols, investigation of the stereochemistry of the allyl selenoxideselenenate <2,3> sigmatropic rearrangement 3: 95 percent / H2 / Rainey Nickel catalyst / 1.5 h With pyridine, sodium tetrahydroborate, hydrogen, nickel in tetrahydrofuran, ethanol, water Davis, Franklin A.; Stringer, Orum D.; McCauley, John P., Jr.; Tetrahedron; vol. 41; nb. 21; (1985); p. 4747 - 4758 View in Reaxys

Se H OH

Rx-ID: 20678429 View in Reaxys 169/176 Yield

Conditions & References Reaction Steps: 2 1: 51 percent / pyridine / tetrahydrofuran; H2O / 6 h / Ambient temperature; asymmetric oxidation of using chiral oxaziridines to optically active allyl alcohols, investigation of the stereochemistry of the allyl selenoxideselenenate <2,3> sigmatropic rearrangement 2: 95 percent / H2 / Rainey Nickel catalyst / 1.5 h With pyridine, hydrogen, nickel in tetrahydrofuran, water Davis, Franklin A.; Stringer, Orum D.; McCauley, John P., Jr.; Tetrahedron; vol. 41; nb. 21; (1985); p. 4747 - 4758 View in Reaxys

H HO

Rx-ID: 1763947 View in Reaxys 170/176 Yield

Conditions & References With sodium hydroxide, dihydrogen peroxide, (-)-Monoisopinocampheylborane, 1.) THF, -25 deg C, 24 h, 2.) 55 deg C, 2 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Brown, Herbert C.; Jadhav, Prabhakar K.; Mandal, Arun K.; Journal of Organic Chemistry; vol. 47; nb. 26; (1982); p. 5074 - 5083 View in Reaxys

Copyright ÂŠ 2018 Elsevier Life Sciences IP Limited except certain content provided by third parties. Reaxys is a trademark of Elsevier Life Sciences IP Limited.

256/258

2018-07-03 17:29:03

H HO

Rx-ID: 2005219 View in Reaxys 171/176 Yield

Conditions & References With methanol, sodium hydroxide, diisopinocamphenylboron chloride, dihydrogen peroxide, 1.) a.) THF, -25 deg C, 72 h, b.) 0 deg C, 24 h, 2.) 55 deg C, 1 h, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Brown, Herbert C.; Desai, Manoj C.; Jadhav, Prabhakar K.; Journal of Organic Chemistry; vol. 47; nb. 26; (1982); p. 5065 5069 View in Reaxys

H O

H OH

Rx-ID: 3049169 View in Reaxys 172/176 Yield 83 %

Conditions & References With toluene-4-sulfonic acid in methanol, Time= 3h Noe, Christian R.; Chemische Berichte; vol. 115; nb. 4; (1982); p. 1591 - 1606 View in Reaxys

H O

Rx-ID: 2681700 View in Reaxys 173/176 Yield

Conditions & References With chiral catalyst, 2.) diethyl ether, -120 deg C, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Mazaleyrat, Jean-Paul; Cram, Donald J.; Journal of the American Chemical Society; vol. 103; nb. 15; (1981); p. 4585 - 4586 View in Reaxys With (2S,2'S)-2-hydroxymethyl-1-<(1-methylpyrrolidine-2-yl)methyl>pyrrolidine, 1.) dimethoxymethane, 30 min, -78 degC, 2.) dimethoxymethane, 1 h, 0 degC, Yield given. Multistep reaction. Yields of byproduct given Mukaiyama, Teruaki; Tetrahedron; vol. 37; nb. 23; (1981); p. 4111 - 4119 View in Reaxys With (2S,2'S)-2-hydroxymethyl-1-<(1-methylpyrrolidine-2-yl)methyl>pyrrolidine, 1.) dimethoxymethane, 30 min, -78 degC, 2.) dimethoxymethane, 1 h, -100 degC, Yield given. Multistep reaction. Yields of byproduct given Mukaiyama, Teruaki; Tetrahedron; vol. 37; nb. 23; (1981); p. 4111 - 4119 View in Reaxys

Copyright ÂŠ 2018 Elsevier Life Sciences IP Limited except certain content provided by third parties. Reaxys is a trademark of Elsevier Life Sciences IP Limited.

257/258

2018-07-03 17:29:03

Grignard's-compound from (+)-bornyl chloride

H OH

Rx-ID: 7245878 View in Reaxys 174/176 Yield

Conditions & References With diethyl ether Vavon; Angelo; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 224; (1947); p. 1435 View in Reaxys

OH H

Raney nickel

H OH

Rx-ID: 7987166 View in Reaxys 175/176 Yield

Conditions & References Hydrogenation Duveen; Kenyon; Journal of the Chemical Society; (1939); p. 1697,1700 View in Reaxys

dl-ethylphenylcarbinol

H OH

Rx-ID: 7245877 View in Reaxys 176/176 Yield

Conditions & References ueber den sauren Bernsteinsaeureester und dessen Brucinsalz Pickard; Kenyon; Journal of the Chemical Society; vol. 99; (1911); p. 55,71; Journal of the Chemical Society; vol. 105; (1914); p. 1121,1123, 1128 View in Reaxys

Copyright ÂŠ 2018 Elsevier Life Sciences IP Limited except certain content provided by third parties. Reaxys is a trademark of Elsevier Life Sciences IP Limited.

258/258

2018-07-03 17:29:03