Methanol → 1alpha,3beta-bis(tert-butyldimethylsilyloxy)-20(S)-hydroxypregna-5,7,16-triene

HRID 1014980ノート

反応式

HRID 1014980 の反応式
[Si:1]([O:8][C@@H:9]1[C@@:28]2([CH3:29])[C:13](=[CH:14][CH:15]=[C:16]3[C@@H:27]2[CH2:26][CH2:25][C@@:24]2([CH3:30])[C@H:17]3[CH2:18][CH:19]=[C:20]2[C:21](=[O:23])[CH3:22])[CH2:12][C@@H:11]([O:31][Si:32]([C:35]([CH3:38])([CH3:37])[CH3:36])([CH3:34])[CH3:33])[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].B1(C)OC(C2C=CC=CC=2)(C2C=CC=CC=2)[C@@H]2N1CCC2.CO>C1(C)C=CC=CC=1>[Si:1]([O:8][C@@H:9]1[C@@:28]2([CH3:29])[C:13](=[CH:14][CH:15]=[C:16]3[C@@H:27]2[CH2:26][CH2:25][C@@:24]2([CH3:30])[C@H:17]3[CH2:18][CH:19]=[C:20]2[C@@H:21]([OH:23])[CH3:22])[CH2:12][C@@H:11]([O:31][Si:32]([C:35]([CH3:36])([CH3:38])[CH3:37])([CH3:33])[CH3:34])[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

参加物

5

反応物 3

HCID 887MethanolHCID 9838490(R)-2-Methyl-CBS-oxazaborolidineHCID 120200821alpha,3beta-Bis(tert-butyldimethylsilyloxy)-20-oxopregna-5,7,16-triene

生成物 1

HCID 120200781alpha,3beta-bis(tert-butyldimethylsilyloxy)-20(S)-hydroxypregna-5,7,16-triene収率 89%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒2 回

反応条件

温度
-20 °C

実験手順

The (1α,3β)-1,3-bis((tert-butyl(dimethyl)silyl)oxy)pregna-5,7,16-trien-20-one synthesized in Example 24 (45.0 g) was dissolved in toluene (240 ml) and then cooled to −20° C., followed by stirring for 30 minutes. Borane-dimethylsulfide complex (22.9 ml) was added to the resulting solution at −20° C. and stirred for 5 minutes. A 1M toluene solution of (R)-2-methyl-CBS-oxazaborolidine (22.9 ml) was further added to the solution at −20° C. and stirred for 1 hour. Methanol was added to the reaction mixture, which was then extracted with ethyl acetate. The extracted solution was dried over anhydrous sodium sulfate and evaporated under reduced pressure to remove the solvent. The resulting residue was purified by silica gel column chromatography (liquid phase: hexane/ethyl acetate=9/1) to give the titled compound (23.3 g, yield 89%).

後処理

  1. additionBorane-dimethylsulfide complex (22.9 ml) was added to the resulting solution at −20° C.
  2. stirringstirred for 5 minutes
  3. stirringstirred for 1 hour
  4. extractionwas then extracted with ethyl acetate
  5. dry with materialThe extracted solution was dried over anhydrous sodium sulfate
  6. customevaporated under reduced pressure
  7. customto remove the solvent
  8. customThe resulting residue was purified by silica gel column chromatography (liquid phase: hexane/ethyl acetate=9/1)

出典と根拠

ORDレコード
ord-da5bcc08717940889cf19ce5e5200b36
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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