Potassium ethanethioate → (2S,4S)-4-acetylthio-2-[4-(2-hydroxyethyl)-1-piperazinylcarbonyl]-1-(4-nitrobenzyloxycarbonyl)pyrrolidine

HRID 362073Notes

Reaction equation

HRID 362073 reaction equation
[C:1]([O-:4])(=[S:3])[CH3:2].[K+].[OH:6][CH2:7][CH2:8][N:9]1[CH2:14][CH2:13][N:12]([C:15]([C@@H:17]2[CH2:21][C@@H:20](OS(C)(=O)=O)[CH2:19][N:18]2[C:27]([O:29][CH2:30][C:31]2[CH:36]=[CH:35][C:34]([N+:37]([O-:39])=[O:38])=[CH:33][CH:32]=2)=[O:28])=[O:16])[CH2:11][CH2:10]1>C(#N)C>[C:1]([S:3][C@@H:20]1[CH2:19][N:18]([C:27]([O:29][CH2:30][C:31]2[CH:32]=[CH:33][C:34]([N+:37]([O-:39])=[O:38])=[CH:35][CH:36]=2)=[O:28])[C@H:17]([C:15]([N:12]2[CH2:13][CH2:14][N:9]([CH2:8][CH2:7][OH:6])[CH2:10][CH2:11]2)=[O:16])[CH2:21]1)(=[O:4])[CH3:2]

Participants

4

Reactant 2

HCID 23670855Potassium ethanethioateHCID 86752003(2S,4R)-2-[4-(2-Hydroxyethyl)-1-piperazinylcarbonyl]-4-methanesulfonyloxy-1-(4-nitrobenzyloxy-carbonyl)pyrrolidine

Product 1

HCID 86752004(2S,4S)-4-acetylthio-2-[4-(2-hydroxyethyl)-1-piperazinylcarbonyl]-1-(4-nitrobenzyloxycarbonyl)pyrrolidineYield 70.3%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
80 °C

Procedure

685 mg of potassium thioacetate were added to a solution of 2.0 g of (2S,4R)-2-[4-(2-hydroxyethyl)-1-piperazinylcarbonyl]-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidine [prepared as described in step 54(a)(ii), 54(a)(ii') and 54(a)(ii") above] in 20 ml of dry acetonitrile, and the resulting mixture was stirred at 80° C. for 5 hours. At the end of this time, the reaction mixture was concentrated by evaporation under reduced pressure, the residue was diluted with 200 ml of ethyl acetate, and the dilute solution was washed with an aqueous solution of sodium chloride; it was then dried over anhydrous magnesium sulfate. The solvent was removed by distillation under reduced pressure, and the residue was purified by column chromatography through silica gel, using a gradient elution method with mixtures of ethyl acetate and methanol ranging from 9:1 to 4:1 by volume as the eluent, to give 1.35 g of the title compound, as a powder.

Workup

  1. concentrationAt the end of this time, the reaction mixture was concentrated by evaporation under reduced pressure
  2. additionthe residue was diluted with 200 ml of ethyl acetate
  3. washthe dilute solution was washed with an aqueous solution of sodium chloride
  4. dry with materialit was then dried over anhydrous magnesium sulfate
  5. customThe solvent was removed by distillation under reduced pressure
  6. customthe residue was purified by column chromatography through silica gel
  7. washa gradient elution method with mixtures of ethyl acetate and methanol ranging from 9:1 to 4:1 by volume as the eluent

Sources & evidence

ORD record
ord-81cbe64e73f542a28e8ce3021198667f
Source dataset
uspto-grants-1999_02
Patent number
US05866564

Reaction notes

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