Potassium ethanethioate → (2s,4s)-1-p-Nitrobenzyloxycarbonyl-2-phthalimidomethyl-4-acetylthiopyrrolidine

HRID 1034487Notes

Reaction equation

HRID 1034487 reaction equation
[N+:1]([C:4]1[CH:35]=[CH:34][C:7]([CH2:8][O:9][C:10]([N:12]2[CH2:16][C@H:15](OS(C)(=O)=O)[CH2:14][C@H:13]2[CH2:22][N:23]2[C:27](=[O:28])[C:26]3=[CH:29][CH:30]=[CH:31][CH:32]=[C:25]3[C:24]2=[O:33])=[O:11])=[CH:6][CH:5]=1)([O-:3])=[O:2].[C:36]([O-:39])(=[S:38])[CH3:37].[K+]>CN(C)C=O>[N+:1]([C:4]1[CH:5]=[CH:6][C:7]([CH2:8][O:9][C:10]([N:12]2[CH2:16][C@@H:15]([S:38][C:36](=[O:39])[CH3:37])[CH2:14][C@H:13]2[CH2:22][N:23]2[C:27](=[O:28])[C:26]3=[CH:29][CH:30]=[CH:31][CH:32]=[C:25]3[C:24]2=[O:33])=[O:11])=[CH:34][CH:35]=1)([O-:3])=[O:2]

Participants

4

Reactant 2

HCID 23670855Potassium ethanethioateHCID 57079827(2s,4r)-1-p-Nitrobenzyloxycarbonyl-2-phthalimidomethyl-4-methanesulfonyloxypyrrolidine

Product 1

HCID 57106506(2s,4s)-1-p-Nitrobenzyloxycarbonyl-2-phthalimidomethyl-4-acetylthiopyrrolidineYield 90.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of (2S,4R)-1-p-nitrobenzyloxycarbonyl-2-phthalimidomethyl-4-methanesulfonyloxypyrrolidine (10 g: 19.88 mmole) and potassium thioacetate (4.54 g: 2 eq.) in dimethylformamide (60 ml) is stirred at 60° C. for 3 hours. The reaction mixture is poured into ice water (200 ml) and filtered. The precipitate is dissolved in ethyl acetate, dried over magnesium sulfate, and concentrated in vacuo. The residue is purified by silica gel column chromatography (toluene: ethyl acetate) to give (2S,4S)-1-p-nitrobenzyloxycarbonyl-2-phthalimidomethyl-4-acetylthiopyrrolidine (8.7 g). Yield: 90%. NMR δ(CDCl3) ppm: 1.65 to 1.97(m, 1H), 2.47 to 2.67(m, 1H), 3.24 to 3.34(q, 1H), 3.73 to 4.24(m, 4H), 4.30 to 4.54(m, 1H), 5.02(dd, J=14 Hz, J=7 Hz, 1H), 5.20(d, J=14 Hz, 1H), 7.42 (d, J=9 Hz, 1H), 7.45(d, J=9 Hz, 1H), 7.60 to 8.86(m, 4H), 8.17(d, J=9 Hz, 2H). IR ν (CHCl3) cm-1 : 1773, 1714, 1605.

Workup

  1. filtrationfiltered
  2. dissolutionThe precipitate is dissolved in ethyl acetate
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated in vacuo
  5. customThe residue is purified by silica gel column chromatography (toluene: ethyl acetate)

Sources & evidence

ORD record
ord-2ff94230fc774241934bc9c5499c30a6
Source dataset
uspto-grants-1994_05
Patent number
US05317016

Reaction notes

Loading…