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

HRID 635029ノート

反応式

HRID 635029 の反応式
[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]

参加物

7

反応物 3

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

生成物 2

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

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

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%).

後処理

  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)

出典と根拠

ORDレコード
ord-c8760235815346079ad1ca264d325066
出典データセット
uspto-grants-2001_02
特許番号
US06184398B2

反応ノート

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