Dimethyl malonate → (2S,4S)-N-allyloxycarbonyl-2-[2,2-bis(methoxycarbonyl)ethyl]-4-triphenylmethylthiopyrrolidine

HRID 1078705노트

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HRID 1078705 반응식
[H-].[Na+].[C:3]([O:10][CH3:11])(=[O:9])[CH2:4][C:5]([O:7][CH3:8])=[O:6].[CH2:12]([O:15][C:16]([N:18]1[CH2:22][C@@H:21]([S:23][C:24]([C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)([C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[CH2:20][C@H:19]1[CH2:43]I)=[O:17])[CH:13]=[CH2:14].S([O-])(O)(=O)=O.[K+]>CN(C)C=O.O>[CH2:12]([O:15][C:16]([N:18]1[CH2:22][C@@H:21]([S:23][C:24]([C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)([C:31]2[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=2)[C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[CH2:20][C@@H:19]1[CH2:43][CH:4]([C:3]([O:10][CH3:11])=[O:9])[C:5]([O:7][CH3:8])=[O:6])=[O:17])[CH:13]=[CH2:14]

참가 물질

7

반응물 4

HCID 7943Dimethyl malonateHCID 24758Sodium hydrideHCID 516920Potassium bisulfateHCID 57112975(2S,4S)-N-allyloxycarbonyl-2-iodomethyl-4-tritylthiopyrrolidine

생성물 1

HCID 57044475(2S,4S)-N-allyloxycarbonyl-2-[2,2-bis(methoxycarbonyl)ethyl]-4-triphenylmethylthiopyrrolidine수율 90.3%

시약·촉매·용매 2

HCID 962Water용매HCID 6228Dimethylformamide용매2회

실험 절차

To an ice-cooled suspension of sodium hydride (60%, in oil suspension, 300 mg, 7.5 mmol) in N,N-dimethylformamide (15 ml) was added dropwise dimethyl malonate (0.92 ml, 8.05 mmol) under a nitrogen atmosphere, and the mixture was stirred for 3.0 min at the same temperature. To the mixture was added a solution of (2S,4S)-N-allyloxycarbonyl-2-iodomethyl-4-triphenylmethylthiopyrrolidine (2.85 g, 5 mmol) in N,N-dimethylformamide (10 ml), and the mixture was stirred for 30 min under ice-cooling, for 1 h at room temperature, and then for 6 h at 60° C. The reaction mixture was poured into a mixture of water (30 ml) and 1N aqueous potassium hydrogensulfate (30 ml), and extracted with ethyl acetate (1×100 ml, 2×50 ml). The combined organic layer was washed successively with water and saturated aqueous sodium chloride, and dried over anhydrous magnesium sulfate. The solvent was removed in vacuo, and the residue was subjected to silica gel column chromatography (hexane-ethyl acetate) to give (2S,4S)-N-allyloxycarbonyl-2-[2,2-bis(methoxycarbonyl)ethyl]-4-triphenylmethylthiopyrrolidine (2.59 g, yield: 90%).

후처리

  1. stirringthe mixture was stirred for 30 min under ice-
  2. waitfor 6 h at 60° C
  3. extractionextracted with ethyl acetate (1×100 ml, 2×50 ml)
  4. washThe combined organic layer was washed successively with water and saturated aqueous sodium chloride
  5. dry with materialdried over anhydrous magnesium sulfate
  6. customThe solvent was removed in vacuo

출처 및 근거

ORD 기록
ord-cf52248fa77c40e2841c4e0936b9db30
출처 데이터셋
uspto-grants-1996_08
특허 번호
US05550121

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