Potassium ethanethioate → (2S,4S)-4-acetylthio-1-allyloxycarbonyl-2-phthalimidomethylpyrrolidine

HRID 1034525Notes

Reaction equation

[CH2:1]([O:4][C:5]([N:7]1[CH2:11][C@H:10](OS(C)(=O)=O)[CH2:9][C@H:8]1[CH2:17][N:18]1[C:22](=[O:23])[C:21]2=[CH:24][CH:25]=[CH:26][CH:27]=[C:20]2[C:19]1=[O:28])=[O:6])[CH:2]=[CH2:3].[C:29]([O-:32])(=[S:31])[CH3:30].[K+]>CN(C)C=O.C(OCC)(=O)C>[C:29]([S:31][C@@H:10]1[CH2:11][N:7]([C:5]([O:4][CH2:1][CH:2]=[CH2:3])=[O:6])[C@H:8]([CH2:17][N:18]2[C:22](=[O:23])[C:21]3=[CH:24][CH:25]=[CH:26][CH:27]=[C:20]3[C:19]2=[O:28])[CH2:9]1)(=[O:32])[CH3:30]

Participants

Conditions

Temperature: 60 °C

Procedure

A solution of (2S,4R)-1-allyloxycarbonyl-2-phthalimidomethyl-4-methanesulfonyloxypyrrolidine (12.4 g: 30.46 mmole) and 90% potassium thioacetate (5.22 g: 45.69 mmole) in dimethylformamide (130 ml) is heated with stirring at 60° C. for 4 hours. The reaction mixture is diluted with ethyl acetate (200 ml) and ice water (200 ml). The organic layer is taken, successively washed with water (3 times) and saturated brine, dried over magnesium sulfate, and concentrated in vacuo. The residue is purified by silica gel chromatography to give crude (2S,4S)-4-acetylthio-1-allyloxycarbonyl-2-phthalimidomethylpyrrolidine (9.33 g). Yield: 81%. NMR δ(CDCl3) ppm: 1.7 to 1.9(m, 1H), 2.33(s, 3H), 2.4 to 2.7(m, 1H), 3.25 (dd, J=6.8 Hz, J=11.4 Hz, 1H), 3.7 to 4.0(m, 2H), 4.0 to 4.2(m, 2H), 4.3 to 4.6(m, 3H), 5.0 to 5.3(m, 2H), 5.7 to 5.9(m, 1H), 7.7(m, 2H), 7.85(m, 2H).

Workup

washsuccessively washed with water (3 times) and saturated brine
dry with materialdried over magnesium sulfate
concentrationconcentrated in vacuo
customThe residue is purified by silica gel chromatography

Sources & evidence

ORD record: ord-130aad0ba1e141fe99a739c9065d85cf
Source dataset: uspto-grants-1994_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05317016

Reaction notes

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