(3S)-3-mercapto-1-(4-nitrobenzyloxycarbonyl)pyrrolidine → (2S,4R)-4-t-butyldimethylsilyloxy-1-(4-nitrobenzyloxycarbonyl)-2-[{(3S)-1-(4-nitrobenzyloxycarbonyl)pyrrolidin-3-ylthio}methyl]pyrrolidine

HRID 1088957노트

반응식

HRID 1088957 반응식
[SH:1][C@H:2]1[CH2:6][CH2:5][N:4]([C:7]([O:9][CH2:10][C:11]2[CH:16]=[CH:15][C:14]([N+:17]([O-:19])=[O:18])=[CH:13][CH:12]=2)=[O:8])[CH2:3]1.C[O-].[Na+].CO.[Si:25]([O:32][C@H:33]1[CH2:37][N:36]([C:38]([O:40][CH2:41][C:42]2[CH:47]=[CH:46][C:45]([N+:48]([O-:50])=[O:49])=[CH:44][CH:43]=2)=[O:39])[C@H:35]([CH2:51]OS(C)(=O)=O)[CH2:34]1)([C:28]([CH3:31])([CH3:30])[CH3:29])([CH3:27])[CH3:26]>CO.C(OCC)(=O)C>[Si:25]([O:32][C@H:33]1[CH2:37][N:36]([C:38]([O:40][CH2:41][C:42]2[CH:43]=[CH:44][C:45]([N+:48]([O-:50])=[O:49])=[CH:46][CH:47]=2)=[O:39])[C@H:35]([CH2:51][S:1][C@H:2]2[CH2:6][CH2:5][N:4]([C:7]([O:9][CH2:10][C:11]3[CH:16]=[CH:15][C:14]([N+:17]([O-:19])=[O:18])=[CH:13][CH:12]=3)=[O:8])[CH2:3]2)[CH2:34]1)([C:28]([CH3:31])([CH3:30])[CH3:29])([CH3:27])[CH3:26]

참가 물질

6

반응물 3

HCID 13219816(3S)-3-mercapto-1-(4-nitrobenzyloxycarbonyl)pyrrolidineHCID 23694274Sodium methanolate methanolHCID 57045968(2S,4R)-4-t-butyldimethylsilyloxy-2-methanesulfonyloxymethyl-1-(4-nitrobenzyloxycarbonyl)pyrrolidine

생성물 1

HCID 57062828(2S,4R)-4-t-butyldimethylsilyloxy-1-(4-nitrobenzyloxycarbonyl)-2-[{(3S)-1-(4-nitrobenzyloxycarbonyl)pyrrolidin-3-ylthio}methyl]pyrrolidine수율 70.6%

시약·촉매·용매 2

HCID 887Methanol용매2회HCID 8857Ethyl Acetate용매

실험 절차

To a solution of (3S)-3-mercapto-1-(4-nitrobenzyloxycarbonyl)pyrrolidine (1.36 g) in methanol (5 ml) was added 28% sodium methoxide-methanol solution (0.97 ml) under ice-cooling and the mixture was stirred at the same temperature for 10 minutes. This solution was added to a solution of (2S, 4R)-4-t-butyldimethylsilyloxy-2-methanesulfonyloxymethyl-1-(4-nitrobenzyloxycarbonyl)pyrrolidine (2 g) in methanol (20 ml). The mixture was stirred at ambient temperature for 3 hours and then at 50°-60° C. for 5 hours. The reaction mixture was evaporated in vacuo to give a residue. The residue was dissolved in ethyl acetate (50 ml). The solution was washed with saturated aqueous sodium chloride, dried over magnesium sulfate and evaporated in vacuo. The resulting residue was chromatographed on silica gel (100 g) eluting with a mixture of n-hexane and ethyl acetate (2:1 v/v). The fractions containing the desired compound were collected and evaporated in vacuo to give (2S, 4R)-4-t-butyldimethylsilyloxy-1-(4 -nitrobenzyloxycarbonyl)-2-[{(3S)-1-(4-nitrobenzyloxycarbonyl)pyrrolidin-3-ylthio}methyl]pyrrolidine (1.95 g).

후처리

  1. temperaturecooling
  2. stirringThe mixture was stirred at ambient temperature for 3 hours
  3. waitat 50°-60° C. for 5 hours
  4. customThe reaction mixture was evaporated in vacuo
  5. customto give a residue
  6. washThe solution was washed with saturated aqueous sodium chloride
  7. dry with materialdried over magnesium sulfate
  8. customevaporated in vacuo
  9. customThe resulting residue was chromatographed on silica gel (100 g)
  10. washeluting with a mixture of n-hexane and ethyl acetate (2:1 v/v)
  11. additionThe fractions containing the desired compound
  12. customwere collected
  13. customevaporated in vacuo

출처 및 근거

ORD 기록
ord-6055db86775e4212851c9fe766fe56b7
출처 데이터셋
uspto-grants-1990_10
특허 번호
US04963543

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