2-Ethoxy-1-(ethoxycarbonyl)-1,2-dihydroquinoline → (2S,4S)-4-acetylthio-1-(4-nitrobenzyloxycarbonyl)-2-(3-allyloxycarbonylphenylcarbamoyl)pyrrolidine

HRID 1059728Notes

Reaction equation

HRID 1059728 reaction equation
[NH2:1][C:2]1[CH:3]=[C:4]([CH:11]=[CH:12][CH:13]=1)[C:5]([O:7][CH2:8][CH:9]=[CH2:10])=[O:6].[C:14]([S:17][CH:18]1[CH2:22][N:21]([C:23]([O:25][CH2:26][C:27]2[CH:32]=[CH:31][C:30]([N+:33]([O-:35])=[O:34])=[CH:29][CH:28]=2)=[O:24])[CH:20]([C:36](O)=[O:37])[CH2:19]1)(=[O:16])[CH3:15].CCOC1N(C(OCC)=O)C2C(=CC=CC=2)C=C1>C1(C)C=CC=CC=1.CCOC(C)=O>[C:14]([S:17][C@@H:18]1[CH2:22][N:21]([C:23]([O:25][CH2:26][C:27]2[CH:32]=[CH:31][C:30]([N+:33]([O-:35])=[O:34])=[CH:29][CH:28]=2)=[O:24])[C@H:20]([C:36](=[O:37])[NH:1][C:2]2[CH:13]=[CH:12][CH:11]=[C:4]([C:5]([O:7][CH2:8][CH:9]=[CH2:10])=[O:6])[CH:3]=2)[CH2:19]1)(=[O:16])[CH3:15]

Participants

6

Reactant 3

HCID 278332-Ethoxy-1-(ethoxycarbonyl)-1,2-dihydroquinolineHCID 135043244-Acetylthio-1-(4-nitrobenzyloxycarbonyl)-2-carboxypyrrolidineHCID 18930599Allyl 3-aminobenzoate

Product 1

HCID 53813961(2S,4S)-4-acetylthio-1-(4-nitrobenzyloxycarbonyl)-2-(3-allyloxycarbonylphenylcarbamoyl)pyrrolidineYield 85.6%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

The above allyl 3-aminobenzoate (26.6 g, 0.15 M) was condensed with 4-acetylthio-1-(4-nitrobenzyloxycarbonyl)-2-carboxypyrrolidine (55.2 g, 0.15 M) by suspension in toluene (750 ml) and addition of EEDQ (44.5 g, 0.18 M). The mixture was stirred overnight, diluted with EtOAc (2 l) and washed with dilute HCl, water and brine. The EtOAc phase was dried and evaporated, and the residue recrystallised from ethanol giving (2S,4S)-4-acetylthio-1-(4-nitrobenzyloxycarbonyl)-2-(3-allyloxycarbonylphenylcarbamoyl)pyrrolidine (67.7 g). Nmr (DMSO-d6): δ 1.93 (quintet, 1H); 2.9 (m, 1H); 3.35 (m, 1H); 3.91-4.14 (m, 2H); 4.49 (quintet, 1H); 4.81 (dd, 2H); 5.22 (dd, 2H); 5.2-5.44 (m, 2H); 5.95-6.10 (m, 1H); 7.47 (d, 2H); 7.66 (t, 2H); 7.8-7.93 (m, 2H); 8.18-8.3 (m, 2H); 10.31 (s, 1H).

Workup

  1. washwashed with dilute HCl, water and brine
  2. dry with materialThe EtOAc phase was dried
  3. customevaporated
  4. customthe residue recrystallised from ethanol

Sources & evidence

ORD record
ord-156c109cdc504263971dd86eff26a1c4
Source dataset
uspto-grants-2003_02
Patent number
US06521612B2

Reaction notes

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