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Sodium borohydride → tert-butyl[(2S)-1-{[tert-butyl(diphenyl)silyl]oxy}-6-hydroxyhexan-2-yl]carbamate

HRID 1524345
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HRID 1524345 반응식
C(OC(=O)N[C:8](=[O:40])[CH2:9][CH2:10][CH2:11][C@H:12]([NH:32][C:33]([O:35][C:36]([CH3:39])([CH3:38])[CH3:37])=[O:34])[CH2:13][O:14][Si:15]([C:28]([CH3:31])([CH3:30])[CH3:29])([C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)(C)(C)C.[BH4-].[Na+]>CC(O)C.O>[C:36]([O:35][C:33](=[O:34])[NH:32][C@@H:12]([CH2:11][CH2:10][CH2:9][CH2:8][OH:40])[CH2:13][O:14][Si:15]([C:28]([CH3:29])([CH3:30])[CH3:31])([C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)[C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1)([CH3:39])([CH3:37])[CH3:38]
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참가 물질

5

반응물 2

HCID 4311764Sodium borohydride2회HCID 89938443tert-butyl[(5S)-5-[(tert-butoxycarbonyl)amino]-6-{[tert-butyl(diphenyl)silyl]oxy}hexanoyl]carbamate

생성물 1

HCID 89938349tert-butyl[(2S)-1-{[tert-butyl(diphenyl)silyl]oxy}-6-hydroxyhexan-2-yl]carbamate수율 62.9%

시약·촉매·용매 2

HCID 962Water용매HCID 3776
Isopropanol
용매

실험 절차

To a stirred solution of the material from Step 3 (128 g, 219 mmol) in 2-propanol (1800 mL) and water (180 mL) at room temperature was added sodium borohydride (8.28 g, 219 mmol). The reaction mixture was stirred at room temperature overnight. Additional 2 g of sodium borohydride was added and stirred at room temperature for an additional 4 hours. The reaction mixture was concentrated to ⅓ volume and diluted with EtOAc and 1 N NaOH (100 mL). The reaction mixture was partitioned, and extracted with EtOAc. The combined organics were washed with brine, dried over MgSO4, filtered and concentrated. The residue was purified by flash chromatography on silica gel using EtOAc-hexanes (0 to 50%) to afford 65 g of the title compound. 1H NMR (CHCl3-d): δ 7.67-7.62 (m, 4H), 7.45-7.35 (m, 6H), 4.72-4.65 (b, 1H), 3.72-3.62 (m, 2H), 3.60-3.52 (m, 3H), 1.62-1.42 (m, 4H), 1.42 (s, 9H), 1.42-1.23 (m, 2H), 1.05 (s, 9H).

후처리

  1. stirringstirred at room temperature for an additional 4 hours
  2. concentrationThe reaction mixture was concentrated
  3. additiondiluted with EtOAc and 1 N NaOH (100 mL)
  4. customThe reaction mixture was partitioned
  5. extractionextracted with EtOAc
  6. washThe combined organics were washed with brine
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe residue was purified by flash chromatography on silica gel

출처 및 근거

ORD 기록
ord-1fc34a7d23f0442fbb866fd0d1bc94d9
출처 데이터셋
uspto-grants-2015_07
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US09079834B2

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