Sodium borohydride → tert-butyl (2S,3S)-1-(tert-butyldimethylsilyloxy)-4-hydroxy-3-(4-(trifluoromethyl)phenyl)butan-2-ylcarbamate

HRID 661092ノート

反応式

HRID 661092 の反応式
[Si:1]([O:8][CH2:9][C@@H:10]([NH:25][C:26](=[O:32])[O:27][C:28]([CH3:31])([CH3:30])[CH3:29])[C@H:11]([C:15]1[CH:20]=[CH:19][C:18]([C:21]([F:24])([F:23])[F:22])=[CH:17][CH:16]=1)/[CH:12]=C/C)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[BH4-].[Na+].C[OH:36].C(Cl)Cl>>[Si:1]([O:8][CH2:9][C@@H:10]([NH:25][C:26](=[O:32])[O:27][C:28]([CH3:31])([CH3:29])[CH3:30])[C@H:11]([C:15]1[CH:20]=[CH:19][C:18]([C:21]([F:23])([F:24])[F:22])=[CH:17][CH:16]=1)[CH2:12][OH:36])([C:4]([CH3:6])([CH3:7])[CH3:5])([CH3:3])[CH3:2]

参加物

4

反応物 3

HCID 4311764Sodium borohydrideHCID 21226129Dichloromethane methanolHCID 86613773tert-butyl (2S,3S,E)-1-(tert-butyldimethylsilyloxy)-3-(4-(trifluoromethyl)phenyl)hex-4-en-2-ylcarbamate

生成物 1

HCID 57634005tert-butyl (2S,3S)-1-(tert-butyldimethylsilyloxy)-4-hydroxy-3-(4-(trifluoromethyl)phenyl)butan-2-ylcarbamate収率 97%

反応条件

温度
-78 °C

実験手順

Tert-butyl (2S,3S,E)-1-(tert-butyldimethylsilyloxy)-3-(4-(trifluoromethyl)phenyl)hex-4-en-2-ylcarbamate (2.0 g, 4.2 mmol) was dissolved in 40 mL of 1:1 MeOH/DCM, and the mixture was chilled to −78° C. Ozone was bubbled through the mixture until a blue color persisted. Nitrogen was then bubbled through the mixture for 15 minutes. NaBH4 (0.80 g, 21 mmol) was added, and the mixture was warmed to room temperature. After 3 hours, the mixture was quenched with aq NH4Cl. The mixture was extracted three times with 50 mL of DCM. The combined organic extracts were dried over MgSO4. Filtration and concentration under reduced pressure afforded tert-butyl (2S,3S)-1-(tert-butyldimethylsilyloxy)-4-hydroxy-3-(4-(trifluoromethyl)phenyl)butan-2-ylcarbamate (1.9 g, 97% yield) as a white solid. 1H NMR (400 MHz, CDCl3) δ ppm 7.56 (d, J=8.03 Hz, 2H) 7.32 (d, J=8.03 Hz, 2H) 4.51 (s, 1H) 4.22-4.16 (m, 1H) 3.90-3.66 (m, 3H) 3.47 (d, J=5.52 Hz, 2H) 3.15-3.20 (m, 1H) 1.45 (s, 9H) 0.84 (s, 9H) 0.01 (s, 3H)-0.01 (s, 3H).

後処理

  1. customOzone was bubbled through the mixture until a blue color
  2. customNitrogen was then bubbled through the mixture for 15 minutes
  3. temperaturethe mixture was warmed to room temperature
  4. customthe mixture was quenched with aq NH4Cl
  5. extractionThe mixture was extracted three times with 50 mL of DCM
  6. dry with materialThe combined organic extracts were dried over MgSO4
  7. filtrationFiltration and concentration under reduced pressure

出典と根拠

ORDレコード
ord-531fb8ce861142b59e3972e866d62440
出典データセット
uspto-grants-2011_12
特許番号
US08084479B2

反応ノート

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