4-(S)-(1-Ethoxycarbonylcyclopropyl)-3-(R)-fluoro-1-[1-(S)-phenylethyl]-2-pyrrolidinethione → 4-(R)-(1-Ethoxycarbonylcyclopropyl)-3-(S)-fluoro-1-[1-(S)-phenylethyl]pyrrolidine

HRID 635079Notes

Reaction equation

HRID 635079 reaction equation
[CH2:1]([O:3][C:4]([C:6]1([C@H:9]2[CH2:13][N:12]([C@H:14]([C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=3)[CH3:15])[C:11](=S)[C@@H:10]2[F:23])[CH2:8][CH2:7]1)=[O:5])[CH3:2]>C(O)C.[Ni]>[CH2:1]([O:3][C:4]([C:6]1([C@@H:9]2[CH2:13][N:12]([C@H:14]([C:16]3[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=3)[CH3:15])[CH2:11][C@H:10]2[F:23])[CH2:7][CH2:8]1)=[O:5])[CH3:2]

Participants

4

Reactant 1

HCID 108606404-(S)-(1-Ethoxycarbonylcyclopropyl)-3-(R)-fluoro-1-[1-(S)-phenylethyl]-2-pyrrolidinethione

Product 1

HCID 219712684-(R)-(1-Ethoxycarbonylcyclopropyl)-3-(S)-fluoro-1-[1-(S)-phenylethyl]pyrrolidineYield 94.7%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 702EthanolSolvent

Procedure

4-(S)-(1-Ethoxycarbonylcyclopropyl)-3-(R)-fluoro-1-[1-(S)-phenylethyl]-2-pyrrolidinethione (4.401 g, 13.12 mmol) was dissolved in anhydrous ethanol (150 ml), and the solution was mixed with Raney nickel (13 ml) and stirred at room temperature for 1 hour. After removing the catalyst by celite filtration (ethanol washing), the resulting filtrate was concentrated under reduced pressure. The thus obtained residue was dissolved in diethyl ether (250 ml), washed with 10% ammonia water (100 ml×5) and saturated brine (100 ml) in that order and then dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure and the resulting residue was subjected to flash silica gel chromatography and eluted with an eluant of n-hexane:ethyl acetate=4:1, to thereby obtain 3.794 g (94.7%) of the title compound as a colorless oil.

Workup

  1. customAfter removing the catalyst
  2. filtrationby celite filtration (ethanol washing)
  3. concentrationthe resulting filtrate was concentrated under reduced pressure
  4. dissolutionThe thus obtained residue was dissolved in diethyl ether (250 ml)
  5. washwashed with 10% ammonia water (100 ml×5) and saturated brine (100 ml) in that order
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationAfter filtration
  8. concentrationthe filtrate was concentrated under reduced pressure
  9. washeluted with an eluant of n-hexane

Sources & evidence

ORD record
ord-c3cee6cb087b484fbf752e4a9c476788
Source dataset
uspto-grants-2001_02
Patent number
US06184388B2

Reaction notes

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