Ethyl Acetate → 1-Pyrrolidinecarboxylic acid, 4-(acetylthio)-2-(hydroxymethyl)-, 2-propen-1-yl ester, (2S,4S)-

HRID 1034529Notes

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][OH:18])=[O:6])[CH:2]=[CH2:3].[C:19]([O-:22])(=[S:21])[CH3:20].[K+].C(OCC)(=O)C>CN(C)C=O>[C:19]([S:21][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][OH:18])[CH2:9]1)(=[O:22])[CH3:20]

Participants

Conditions

Temperature: 65 °C

Procedure

A solution of (2S,4R)-1-allyloxycarbonyl-4-methanesulfonyloxypyrrolidine-2-methanol (19.32 g: 69.17 mmole) and 90% potassium thioacetate (10.73 g: 89.9 mmole) in dimethylformamide (217 ml) is heated with stirring at 65° C. for 5 hours. To the reaction mixture ethyl acetate (200 ml) and ice water (200 ml) are added. The organic layer is taken, successively washed with aqueous 0.05N-sodium hydroxide, 0.1N-hydrochloric acid, water and saturated brine, dried over magnesium sulfate, and concentrated in vacuo. The residue is purified by silica gel chromatography to give (2S,4S)-4-acetylthio-1-allyloxycarbonylpyrrolidine-2-methanol (15.34 g). Yield: 90%. NMR δ(CDCl3) ppm: 1.5 to 1.7(m, 1H), 2.34(s, 3H), 2.4 to 2.6(m, 1H), 3.19(dd, J=8.0 Hz, J=11.5 Hz, 1H), 3.6 to 3.8(m, 2H), 3.8 to 4.0(m, 1H), 4.0 to 4.2(m, 2H), 4.6(m, 2H), 5.2 to 5.4(m, 2H), 5.8 to 6.1(m, 1H).

Workup

washsuccessively washed with aqueous 0.05N-sodium hydroxide, 0.1N-hydrochloric acid, water 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-6db95aa8b4ae46d5be79c97d672e41a0
Source dataset: uspto-grants-1994_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05317016

Reaction notes

Loading…