Potassium ethanethioate → tert-Butyl (2R,4S)-4-(acetylsulfanyl)-2-(hydroxymethyl)pyrrolidine-1-carboxylate

HRID 1034509Notes

Reaction equation

HRID 1034509 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:12][C@H:11](OS(C)(=O)=O)[CH2:10][C@@H:9]1[CH2:18][OH:19])=[O:7])([CH3:4])([CH3:3])[CH3:2].[C:20]([O-:23])(=[S:22])[CH3:21].[K+]>CN(C)C=O.C(OCC)(=O)C>[C:20]([S:22][C@@H:11]1[CH2:12][N:8]([C:6]([O:5][C:1]([CH3:2])([CH3:3])[CH3:4])=[O:7])[C@@H:9]([CH2:18][OH:19])[CH2:10]1)(=[O:23])[CH3:21]

Participants

5

Reactant 2

HCID 23670855Potassium ethanethioateHCID 53830029(2R,4R)-1-t-butoxycarbonyl-4-methanesulfonyloxypyrrolidine-2-methanol

Product 1

HCID 57080293tert-Butyl (2R,4S)-4-(acetylsulfanyl)-2-(hydroxymethyl)pyrrolidine-1-carboxylate

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

(2R,4R)-1-t-Butoxycarbonyl-4-methanesulfonyloxypyrrolidine-2-methanol (i.e., a substrate) and potassium thioacetate (KSAc) are dissolved in dimethylformamide (DMF), and the mixture is stirred. The conditions for this reaction are shown in Table 1, Step A-5. The reaction mixture is diluted with ethyl acetate, and ice water is added. The organic layer is taken, successively washed with aqueous sodium hydroxide, hydrochloric acid, water and saturated brine, dried over magnesium sulfate, and concentrated in vacuo. The residue is purified by silica gel chromatography to give (2R,4S)-4-acetylthio-1-t-butoxycarbonylpyrrolidine-2-methanol. NMR δ(CDCl3) ppm: 1.47(s, 9H), 2.05(t, 2H), 2.34(s, 3H), 3.0 to 3.3(m, 1H), 3.40(dd, J=11.6 Hz, J=5.2 Hz, 1H), 3.5 to 3.9(m, 3H), 3.9 to 4.2(m, 2H).

Workup

  1. additionis added
  2. washsuccessively washed with aqueous sodium hydroxide, hydrochloric acid, water and saturated brine
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated in vacuo
  5. customThe residue is purified by silica gel chromatography

Sources & evidence

ORD record
ord-74a9d68d21174a45900987bb8da00703
Source dataset
uspto-grants-1994_05
Patent number
US05317016

Reaction notes

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