Dichloromethane → (RS)-5-(4-Benzyloxy-phenyl)-4-tertbutoxycarbonylamino-pent-2-enoic acid methyl ester

HRID 852878

반응식

HRID 852878 반응식
C(OP([CH2:9][C:10]([O:12][CH3:13])=[O:11])(OCC)=O)C.[C:14]([O:18][C:19](=[O:39])[NH:20][CH:21]([CH2:24][C:25]1[CH:30]=[CH:29][C:28]([O:31][CH2:32][C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)=[CH:27][CH:26]=1)[CH:22]=O)([CH3:17])([CH3:16])[CH3:15].[OH-].[Na+].[CH2:42](Cl)Cl>[I-].C([N+](CCCC)(CCCC)CCCC)CCC>[CH2:13]([O:12][C:10](=[O:11])[CH:9]=[CH:22][CH:21]([NH:20][C:19]([O:18][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:39])[CH2:24][C:25]1[CH:30]=[CH:29][C:28]([O:31][CH2:32][C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)=[CH:27][CH:26]=1)[CH3:42].[CH3:13][O:12][C:10](=[O:11])[CH:9]=[CH:22][CH:21]([NH:20][C:19]([O:18][C:14]([CH3:15])([CH3:17])[CH3:16])=[O:39])[CH2:24][C:25]1[CH:26]=[CH:27][C:28]([O:31][CH2:32][C:33]2[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=2)=[CH:29][CH:30]=1

참가 물질

7

반응물 4

HCID 6344Dichloromethane2회HCID 14798Sodium HydroxideHCID 66113Methyl diethylphosphonoacetateHCID 10904373tert-butyl N-[1-oxo-3-(4-phenylmethoxyphenyl)propan-2-yl]carbamate

생성물 2

HCID 69415650(RS)-5-(4-Benzyloxy-phenyl)-4-tertbutoxycarbonylamino-pent-2-enoic acid methyl esterHCID 69416006(RS)-5-(4-Benzyloxy-phenyl)-4-tertbutoxycarbonylamino-pent-2-enoic acid ethyl ester

시약·촉매·용매 1

HCID 67553Tetrabutylammonium Iodide촉매

실험 절차

A solution of triethyl phosphonoacetate or methyl diethylphosphonoacetate (5.19 mmol) and (RS)-[1-(4-Benzyloxy-benzyl)-2-oxo-ethyl]-carbamic acid tert-butyl ester (1.843 g, 5.19 mmol) in DCM (5 mL) was added dropwise to a vigorously stirred mixture of 50% aq. NaOH (30 mL) and 50 mL DCM containing tetrabutylammonium iodide (1.0 g). After 3 hr, the layers were separated and the organic phase was washed with water (20 mL) and brine (10 mL) then dried (Na2SO4) and evaporated. The crude material was chromatographed (silica gel, 1:4 EtOAc/petroleum) to give either (RS)-5-(4-Benzyloxy-phenyl)-4-tertbutoxycarbonylamino-pent-2-enoic acid ethyl ester 77 or (RS)-5-(4-Benzyloxy-phenyl)-4-tertbutoxycarbonylamino-pent-2-enoic acid methyl ester RS-40 (˜85% yield in each case). Compound 77: 1H nmr (CDCl3) δ 1.28 (t, J=7.1 Hz, 3H), 1.40 (s, 9H), 2.84 (br d, J=6.2 Hz, 2H), 4.19 (q, J=7.1 Hz, 2H), 4.52 (br s, 2H), 5.05 (s, 2H), 5.86 (dd, J=1.5, 15.7 Hz, 1H), 6.91 (dd, J=4.8, 15.6 Hz, 1H), 6.92 (d, J=8.6 Hz, 2H), 7.09 (d J=8.7 Hz, 2H), 7.32-7.45 (m, 5H). 13C nmr (CDCl3) δ 66.1, 157.7, 154.9, 147.7, 137.0, 130.4, 128.6, 127.9, 127.4, 121.0, 115.1, 114.9, 79.8, 70.0, 60.4, 52.4, 40.0, 28.3, 14.2. Compound RS-40: 1H NMR (CDCl3) δ 1.40 (s, 9H), 2.80 (m, 2H), 3.70 (s, 3H), 4.52 (br s, 2H), 5.05 (s, 2H), 5.83 (d, J=15 Hz, 1H), 6.88 (d, J=8.7 Hz, 2H), 6.88 (d, J=15 Hz, 1H), 7.07 (d, J=8.7 Hz, 2H), 7.28-7.48 (m, 5H). 13C NMR (CDCl3) δ 28.5, 40.1, 51.8, 52.6, 70.2, 80.0, 115.1, 120.8, 127.6, 128.1, 128.7, 130.6, 137.1, 148.2, 155.1, 157.9, 166.8.

후처리

  1. customthe layers were separated
  2. washthe organic phase was washed with water (20 mL) and brine (10 mL)
  3. dry with materialthen dried (Na2SO4)
  4. customevaporated
  5. customThe crude material was chromatographed (silica gel, 1:4 EtOAc/petroleum)

출처 및 근거

ORD 기록
ord-aefc3fa9d2ff45bc9595f1567d1a39a3
출처 데이터셋
uspto-grants-2007_08
특허 번호
US07253194B2

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