Potassium ethanethioate → 17-Acetylthiomethyl-1alpha,3beta-bis(tert-butyldimethylsilyloxy)androsta-5,7,16-triene

HRID 1014967ノート

反応式

HRID 1014967 の反応式
[Si:1]([O:8][C@@H:9]1[C@@:26]2([CH3:27])[C:13](=[CH:14][CH:15]=[C:16]3[C@@H:25]2[CH2:24][CH2:23][C@@:21]2([CH3:22])[C@H:17]3[CH2:18][CH:19]=[C:20]2[CH2:28]Br)[CH2:12][C@@H:11]([O:30][Si:31]([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:33])[CH3:32])[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[C:38]([O-:41])(=[S:40])[CH3:39].[K+]>CC(C)=O.CCCCCC>[C:38]([S:40][CH2:28][C:20]1[C@:21]2([CH2:23][CH2:24][C@H:25]3[C:16](=[CH:15][CH:14]=[C:13]4[C@:26]3([CH3:27])[C@@H:9]([O:8][Si:1]([C:4]([CH3:6])([CH3:5])[CH3:7])([CH3:3])[CH3:2])[CH2:10][C@H:11]([O:30][Si:31]([C:34]([CH3:36])([CH3:37])[CH3:35])([CH3:33])[CH3:32])[CH2:12]4)[C@@H:17]2[CH2:18][CH:19]=1)[CH3:22])(=[O:41])[CH3:39]

参加物

5

反応物 2

HCID 23670855Potassium ethanethioateHCID 673014911alpha,3beta-Bis(tert-butyldimethylsilyloxy)-17-(bromomethyl)androsta-5,7,16-triene

生成物 1

HCID 8658997017-Acetylthiomethyl-1alpha,3beta-bis(tert-butyldimethylsilyloxy)androsta-5,7,16-triene収率 64%

試薬・触媒・溶媒 2

HCID 180Acetone溶媒HCID 8058Hexane溶媒

実験手順

To a solution of 1α,3β-bis(tert-butyldimethylsilyloxy)-17-(hydroxymethyl)androsta-5,7,16-triene (100 mg, 0.183 mmol), triphenylphosphine (96.0 mg, 0.366 mmol) and imidazole (49.8 mg, 0.732 mmol) in dichloromethane (2 ml), N-bromosuccinimide (65.1 mg, 0.366 mmol) was added at 0° C. and stirred at room temperature. After 1 hour, hexane was added to the reaction mixture, which was then washed with water and saturated aqueous sodium chloride. After drying over anhydrous magnesium sulfate, the solvent was removed under reduced pressure to give a mixture (150 mg) containing 1α,3β-bis(tert-butyldimethylsilyloxy)-17-(bromomethyl)androsta-5,7,16-triene. This mixture was dissolved in acetone (1.5 ml), followed by addition of potassium thioacetate (31.4 mg, 0.275 mmol) and stirring for 30 minutes. The reaction mixture was diluted with hexane and filtered. The resulting filtrate was evaporated under reduced pressure to remove the solvent and the residue was purified by preparative thin layer chromatography (0.5 mm×2 plates, hexane:ethyl acetate=20:1, developed once) to give the titled compound (70.2 mg, 64%) as a colorless oil.

後処理

  1. filtrationfiltered
  2. customThe resulting filtrate was evaporated under reduced pressure
  3. customto remove the solvent
  4. customthe residue was purified by preparative thin layer chromatography (0.5 mm×2 plates, hexane

出典と根拠

ORDレコード
ord-4a993fa913d6426898c5f265b155dfcd
出典データセット
uspto-grants-2011_07
特許番号
US07985744B2

反応ノート

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