Water → benzyl (2RS,3SR)-3-hydroxy-2,4,4-trimethylpyrrolidine-1-carboxylate

HRID 906977ノート

反応式

HRID 906977 の反応式
[Si]([O:8][CH:9]([C:23]([CH3:27])([CH3:26])[CH2:24]O)[CH:10]([NH:12][C:13](=[O:22])[O:14][CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[CH3:11])(C(C)(C)C)(C)C.C(N(CC)CC)C.S(Cl)(C)(=O)=O.O>C1COCC1>[OH:8][CH:9]1[C:23]([CH3:24])([CH3:26])[CH2:27][N:12]([C:13]([O:14][CH2:15][C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=2)=[O:22])[CH:10]1[CH3:11]

参加物

6

反応物 4

HCID 962WaterHCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 59273056Benzyl [2-(tert-butyldimethylsilyloxy)-4-hydroxy-1,3,3-trimethylbutyl]carbamate

生成物 1

HCID 67390300benzyl (2RS,3SR)-3-hydroxy-2,4,4-trimethylpyrrolidine-1-carboxylate収率 92%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

A solution (20 mL) of benzyl [2-(tert-butyldimethylsilyloxy)-4-hydroxy-1,3,3-trimethylbutyl]carbamate (1.38 g) and triethylamine (0.73 mL) in THF was added mesyl chloride (0.352 mL) at 0° C., and the mixture was stirred at 0° C. for 45 min. The reaction mixture was added to water, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. To a solution (20 mL) of the residue in THF was added 1M potassium tert-butoxide—THF solution (3.8 mL). After stirring at room temperature for 1 hr, water was added and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. To a solution (10 mL) of the residue in THF was added 1M tetrabutylammonium fluoride—THF solution (4 mL), and the mixture was stirred at room temperature for 17 hr. The reaction mixture was added to water, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane/ethyl acetate=50/1→1/2) to give the title compound as a colorless solid (yield: 842 mg, yield: 92%).

後処理

  1. extractionthe mixture was extracted with ethyl acetate
  2. washThe extract was washed with saturated brine
  3. dry with materialdried over anhydrous magnesium sulfate
  4. concentrationconcentrated under reduced pressure
  5. additionTo a solution (20 mL) of the residue in THF was added 1M potassium tert-butoxide—THF solution (3.8 mL)
  6. stirringAfter stirring at room temperature for 1 hr
  7. additionwater was added
  8. extractionthe mixture was extracted with ethyl acetate
  9. washThe extract was washed with saturated brine
  10. dry with materialdried over anhydrous magnesium sulfate
  11. concentrationconcentrated under reduced pressure
  12. additionTo a solution (10 mL) of the residue in THF was added 1M tetrabutylammonium fluoride—THF solution (4 mL)
  13. stirringthe mixture was stirred at room temperature for 17 hr
  14. additionThe reaction mixture was added to water
  15. extractionthe mixture was extracted with ethyl acetate
  16. washThe extract was washed with saturated brine
  17. dry with materialdried over anhydrous magnesium sulfate
  18. concentrationconcentrated under reduced pressure
  19. customThe residue was purified by silica gel column chromatography (eluent: hexane/ethyl acetate=50/1→1/2)

出典と根拠

ORDレコード
ord-74688b5e93f146f597826dcbeaa9da7d
出典データセット
uspto-grants-2011_09
特許番号
US08013008B2

反応ノート

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