Benzyl Alcohol → Ethyl 2-(benzyloxycarbonylamino)-1-(tert-butyldimethylsilyloxy)cyclopropanecarboxylate

HRID 241793노트

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HRID 241793 반응식
[Si:1]([O:8][C:9]1([C:15]([O:17][CH2:18][CH3:19])=[O:16])[CH2:11][CH:10]1C(O)=O)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].C1C=CC(P([N:34]=[N+]=[N-])(C2C=CC=CC=2)=O)=CC=1.[CH2:37]([OH:44])[C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1.C([O:48][CH2:49]C)(=O)C>C1(C)C=CC=CC=1>[CH2:18]([O:17][C:15]([C:9]1([O:8][Si:1]([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:2])[CH3:3])[CH2:11][CH:10]1[NH:34][C:49]([O:44][CH2:37][C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1)=[O:48])=[O:16])[CH3:19]

참가 물질

6

반응물 4

HCID 244Benzyl AlcoholHCID 8857Ethyl AcetateHCID 199401P,P-Diphenylphosphinic azideHCID 667282072-(Tert-butyldimethylsilyloxy)-2-(ethoxycarbonyl)cyclopropanecarboxylic acid

생성물 1

HCID 66728242Ethyl 2-(benzyloxycarbonylamino)-1-(tert-butyldimethylsilyloxy)cyclopropanecarboxylate수율 30%

시약·촉매·용매 1

HCID 1140Toluene용매

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온도
0 °C

실험 절차

A mixture of 2-(tert-butyldimethylsilyloxy)-2-(ethoxycarbonyl)cyclopropanecarboxylic acid (4b, 0.335 g, 1.16 mmol) in toluene (5 mL) under nitrogen was treated with Hüenig's base (0.260 mL, 1.51 mmol) and the mixture was cooled to 0° C. After this time, DPPA (0.324 mL, 1.51 mmol) was added and the mixture was heated at 90° C. for 30 min, followed by the addition of benzyl alcohol (0.155 mL. 1.51 mmol). After 15 h, the mixture was cooled, diluted with ethyl acetate (75 mL), and washed sequentially with 10% citric acid (2×50 mL), water (50 mL), and saturated NaHCO3 (50 mL). The organic phase was dried (MgSO4), filtered, and concentrated. The residue was purified by silica gel chromatography eluting with 10% EtOAc/hexanes to 100% EtOAc to afford the title compound as a clear oil (0.146 g, 30%): 1H NMR (300 MHz, CDCl3) δ 7.34-7.30 (m, 5H), 5.40-5.38 (m, 1H), 5.21-5.00 (m, 2H), 4.29-4.18 (m, 2H), 4.16-4.09 (m, 1H), 1.50-1.47 (m, 2H), 1.30 (t, J=7.2 Hz, 3H), 0.88 (s, 9H), 0.26-0.07 (m, 6H); Multimode (APCI+ESI) MS m/z 295 [M+H]+.

후처리

  1. temperaturethe mixture was heated at 90° C. for 30 min
  2. temperaturethe mixture was cooled
  3. washwashed sequentially with 10% citric acid (2×50 mL), water (50 mL), and saturated NaHCO3 (50 mL)
  4. dry with materialThe organic phase was dried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe residue was purified by silica gel chromatography
  8. washeluting with 10% EtOAc/hexanes to 100% EtOAc

출처 및 근거

ORD 기록
ord-89c395c43c6d4e33b627098ad0a8071a
출처 데이터셋
uspto-grants-2014_02
특허 번호
US08653042B2

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