2-Benzhydryl-3-quinuclidinone → (2S,3S)-2-benzhydrylquinuclidin-3-ol
反応式
[CH:1]([CH:14]1[C:19](=[O:20])[CH:18]2[CH2:21][CH2:22][N:15]1[CH2:16][CH2:17]2)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CC(C)([O-])C.[K+].[H][H]>CC(O)C>[CH:1]([C@H:14]1[C@@H:19]([OH:20])[CH:18]2[CH2:17][CH2:16][N:15]1[CH2:22][CH2:21]2)([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1参加物
5
実験手順
397.7 mg (1.30 mmol) of a racemic mixture of 2-benzhydrylquinuclidin-3-one (1-2) and 1.2 mg (1.3 μmol) of (S)-1,1′-binaphthyl-2,2′-bis(diphenyl)phosphine ruthenium (II) dichloride (R,R)-hexane-2,5-diamine complex were placed in an autoclave in which the inside had been replaced with argon. After adding 6.4 ml of 2-propanol thereto and degassing, 0.13 mL (0.13 mmol) of a 2-propanol solution of potassium tert-butoxide (1.0 M) were added thereto followed by stirring for 18 hours at 20 to 25° C. at a hydrogen pressure of 1.0 MPa. After concentrating the reaction solution, analysis of the crude purification product by 1H-NMR indicated that only the syn form had been formed. The reaction solution was then purified by silica gel column chromatography (developing solvent: n-hexane:ethyl acetate=3:1 (volume ratio)) to obtain 382 mg (1.30 mmol, yield: 96%) of (2S,3S)-2-benzhydrylquinuclidin-3-ol (3-2). The optical purity of this substance as measured by high-performance liquid chromatography (eluent: acetonitrile:0.02 M aqueous disodium hydrogen phosphate=6:4 (volume ratio), column: CHIRALCEL OD-RH, Daicel Chemical Industries, Ltd.) was 96% ee.