Sodium hydride → (2S,4S)-1-allyloxycarbonyl-2-(2-fluoroethyloxymethyl)-4-[(1-thioxopropyl)thio]pyrrolidine

HRID 1464721Notes

Reaction equation

HRID 1464721 reaction equation
[H-].[Na+].[C:3]([SH:7])(=[S:6])[CH2:4][CH3:5].[CH2:8]([O:11][C:12]([N:14]1[CH2:18][C@H:17](OS(C)(=O)=O)[CH2:16][C@H:15]1[CH2:24][O:25][CH2:26][CH2:27][F:28])=[O:13])[CH:9]=[CH2:10]>O1CCCC1>[CH2:8]([O:11][C:12]([N:14]1[CH2:18][C@@H:17]([S:6][C:3](=[S:7])[CH2:4][CH3:5])[CH2:16][C@H:15]1[CH2:24][O:25][CH2:26][CH2:27][F:28])=[O:13])[CH:9]=[CH2:10]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 10176109Propanedithioic AcidHCID 57165653(2S,4R)-1-allyloxycarbonyl-2-(2-fluoroethyloxymethyl)-4-methylsulfonyloxypyrrolidine

Product 1

HCID 57310918(2S,4S)-1-allyloxycarbonyl-2-(2-fluoroethyloxymethyl)-4-[(1-thioxopropyl)thio]pyrrolidineYield 60%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a suspension of sodium hydride (60% in oil, 2.0 g) in anhydrous tetrahydrofuran (50 ml) was added propanedithioic acid (5.0 g) with ice-cooling. A solution of (2S,4R)-1-allyloxycarbonyl-2-(2-fluoroethyloxymethyl)-4-methylsulfonyloxypyrrolidine (16.25 g) in anhydrous tetrahydrofuran (50 ml) was added dropwise to the mixture and the mixture was heated at 60°-70° C. for 4 hours. The solution was poured into ice-water (100 ml) and extracted with diethyl ether. The organic layer was washed with 1N aqueous sodium hydroxide solution (50 ml) and brine, dried, and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel [n-hexane-ethyl acetate (10:1, V/V)] to afford (2S,4S)-1-allyloxycarbonyl-2-(2-fluoroethyloxymethyl)-4-[(1-thioxopropyl)thio]pyrrolidine (9.47 g).

Workup

  1. temperaturecooling
  2. temperaturethe mixture was heated at 60°-70° C. for 4 hours
  3. extractionextracted with diethyl ether
  4. washThe organic layer was washed with 1N aqueous sodium hydroxide solution (50 ml) and brine
  5. customdried
  6. customevaporated under reduced pressure
  7. customThe residue was purified by column chromatography on silica gel [n-hexane-ethyl acetate (10:1, V/V)]

Sources & evidence

ORD record
ord-7b7619e10011423fa6aec898a94e952e
Source dataset
uspto-grants-1994_04
Patent number
US05306816

Reaction notes

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