Sodium borohydride → 1alpha,3beta-bis(tert-butyldimethylsilyloxy)-20(R)-hydroxypregna-5,7,16-triene

HRID 635029노트

반응식

HRID 635029 반응식
[C:1]([Si:5]([CH3:38])([CH3:37])[O:6][C@@H:7]1[C@@:26]2([CH3:27])[C:11](=[CH:12][CH:13]=[C:14]3[C@@H:25]2[CH2:24][CH2:23][C@@:22]2([CH3:28])[C@H:15]3[CH2:16][CH:17]=[C:18]2[C:19](=[O:21])[CH3:20])[CH2:10][C@@H:9]([O:29][Si:30]([C:33]([CH3:36])([CH3:35])[CH3:34])([CH3:32])[CH3:31])[CH2:8]1)([CH3:4])([CH3:3])[CH3:2].O.O.O.O.O.O.O.[Cl-].[Ce+3].[Cl-].[Cl-].[BH4-].[Na+]>CO.O1CCCC1>[Si:5]([O:6][C@@H:7]1[C@@:26]2([CH3:27])[C:11](=[CH:12][CH:13]=[C:14]3[C@@H:25]2[CH2:24][CH2:23][C@@:22]2([CH3:28])[C@H:15]3[CH2:16][CH:17]=[C:18]2[C@H:19]([OH:21])[CH3:20])[CH2:10][C@@H:9]([O:29][Si:30]([C:33]([CH3:34])([CH3:36])[CH3:35])([CH3:31])[CH3:32])[CH2:8]1)([C:1]([CH3:4])([CH3:3])[CH3:2])([CH3:38])[CH3:37].[Si:5]([O:6][C@@H:7]1[C@@:26]2([CH3:27])[C:11](=[CH:12][CH:13]=[C:14]3[C@@H:25]2[CH2:24][CH2:23][C@@:22]2([CH3:28])[C@H:15]3[CH2:16][CH:17]=[C:18]2[C@@H:19]([OH:21])[CH3:20])[CH2:10][C@@H:9]([O:29][Si:30]([C:33]([CH3:34])([CH3:36])[CH3:35])([CH3:31])[CH3:32])[CH2:8]1)([C:1]([CH3:4])([CH3:3])[CH3:2])([CH3:38])[CH3:37]

참가 물질

7

반응물 3

HCID 4311764Sodium borohydrideHCID 120200821alpha,3beta-Bis(tert-butyldimethylsilyloxy)-20-oxopregna-5,7,16-trieneHCID 21585214Cerium trichloride heptahydrate

생성물 2

HCID 120200781alpha,3beta-bis(tert-butyldimethylsilyloxy)-20(S)-hydroxypregna-5,7,16-triene수율 18%HCID 120200831alpha,3beta-bis(tert-butyldimethylsilyloxy)-20(R)-hydroxypregna-5,7,16-triene수율 73%

시약·촉매·용매 2

HCID 887Methanol용매HCID 8028Tetrahydrofuran용매

실험 절차

To a solution of 1α,3β-bis(tert-butyldimethyl-silyloxy)-20-oxopregna-5,7,16-triene (93 mg, 0.167 mmol) and cerium (III) chloride heptahydrate (93 mg, 0.251 mmol) in methanol (1.5 ml) and tetrahydrofuran (6 ml) cooled at 0° C. was gradually added sodium borohydride (32 mg, 0.835 mmol). The reaction solution was stirred at room temperature for one hour, then concentrated under reduced pressure and the residue was taken into water and extracted with ethyl acetate. The organic layer was washed with brine and then dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting residue was purified by preparative thin layer chromatography (0.5 mm×2, hexane:ethyl acetate=10:1, developed three times) to give the title compound as a colorless solid (68.2 mg, 73%) and 1α,3β-bis(tert-butyldimethylsilyloxy)-20(S)-hydroxypregna-5,7,16-triene (17.0 mg, 18%).

후처리

  1. concentrationconcentrated under reduced pressure
  2. extractionextracted with ethyl acetate
  3. washThe organic layer was washed with brine
  4. dry with materialdried over magnesium sulfate
  5. distillationthe solvent was distilled off under reduced pressure
  6. customThe resulting residue was purified by preparative thin layer chromatography (0.5 mm×2, hexane:ethyl acetate=10:1, developed three times)

출처 및 근거

ORD 기록
ord-c8760235815346079ad1ca264d325066
출처 데이터셋
uspto-grants-2001_02
특허 번호
US06184398B2

반응 노트

불러오는 중…