3-(R)-Tert-butyldimethylsilyloxy-4-(S)-(1-ethoxycarbonylcyclopropyl)-1-[1-(S)-phenylethyl]-2-pyrrolidinethione → 3-(S)-Tert-butyldimethylsilyloxy-4-(R)-(1-ethoxycarbonylcyclopropyl)-1-[1-(S)-phenylethyl]pyrrolidine

HRID 635072Notes

Reaction equation

HRID 635072 reaction equation
[Si:1]([O:8][C@@H:9]1[C@@H:13]([C:14]2([C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH2:16][CH2:15]2)[CH2:12][N:11]([C@H:22]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[CH3:23])[C:10]1=S)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]>C(O)C.[Ni]>[Si:1]([O:8][C@H:9]1[C@H:13]([C:14]2([C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH2:15][CH2:16]2)[CH2:12][N:11]([C@H:22]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[CH3:23])[CH2:10]1)([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:3])[CH3:2]

Participants

4

Reactant 1

HCID 219712643-(R)-Tert-butyldimethylsilyloxy-4-(S)-(1-ethoxycarbonylcyclopropyl)-1-[1-(S)-phenylethyl]-2-pyrrolidinethione

Product 1

HCID 219712663-(S)-Tert-butyldimethylsilyloxy-4-(R)-(1-ethoxycarbonylcyclopropyl)-1-[1-(S)-phenylethyl]pyrrolidineYield 74%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 702EthanolSolvent

Procedure

3-(R)-Tert-butyldimethylsilyloxy-4-(S)-(1-ethoxycarbonylcyclopropyl)-1-[1-(S)-phenylethyl]-2-pyrrolidinethione (7.96 g, 17.74 mmol) was dissolved in anhydrous ethanol (490 ml), and the solution was mixed with Raney nickel (25 ml) and heated under reflux for 40 minutes. After removing the catalyst by celite filtration (ethanol washing), the resulting filtrate was concentrated under reduced pressure. The thus obtained residue was dissolved in chloroform (400 ml), washed with 10% ammonia water (300 ml), water (300 ml) and saturated brine (300 ml) in that order and then dried over anhydrous sodium 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=6:1, to thereby obtain 5.48 g (74%) of the title compound as a colorless oil.

Workup

  1. temperatureheated
  2. temperatureunder reflux for 40 minutes
  3. customAfter removing the catalyst
  4. filtrationby celite filtration (ethanol washing)
  5. concentrationthe resulting filtrate was concentrated under reduced pressure
  6. dissolutionThe thus obtained residue was dissolved in chloroform (400 ml)
  7. washwashed with 10% ammonia water (300 ml), water (300 ml) and saturated brine (300 ml) in that order
  8. dry with materialdried over anhydrous sodium sulfate
  9. filtrationAfter filtration
  10. concentrationthe filtrate was concentrated under reduced pressure
  11. washeluted with an eluant of n-hexane

Sources & evidence

ORD record
ord-892842a6763340f992fab3e915cfde80
Source dataset
uspto-grants-2001_02
Patent number
US06184388B2

Reaction notes

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