Ammonium Chloride → (NE,S)-N-[(3aR,6aS)-2-benzyl-1,3,3a,5,6,6a-hexahydrocyclopenta[c]pyrrol-4-ylidene]-2-methylpropane-2-sulfinamide

HRID 2363441Notes

Reaction equation

HRID 2363441 reaction equation
[CH2:1]([N:8]1[CH2:12][CH:11]2[C:13](=O)[CH2:14][CH2:15][CH:10]2[CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH3:17][C:18]([S@@:21]([NH2:23])=[O:22])([CH3:20])[CH3:19].[Cl-].[NH4+]>O1CCCC1.[O-]CC.[O-]CC.[O-]CC.[O-]CC.[Ti+4]>[CH2:1]([N:8]1[CH2:12][C@@H:11]2/[C:13](=[N:23]/[S@:21]([C:18]([CH3:20])([CH3:19])[CH3:17])=[O:22])/[CH2:14][CH2:15][C@@H:10]2[CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:1]([N:8]1[CH2:12][C@H:11]2/[C:13](=[N:23]/[S@:21]([C:18]([CH3:20])([CH3:19])[CH3:17])=[O:22])/[CH2:14][CH2:15][C@H:10]2[CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 3

HCID 25517Ammonium ChlorideHCID 11355477tert-Butylsulfinamide, (S)-(-)-HCID 134637692-Benzylhexahydrocyclopenta[c]pyrrol-4(1H)-one

Product 2

HCID 87063925(NE,S)-N-[(3aR,6aS)-2-benzyl-1,3,3a,5,6,6a-hexahydrocyclopenta[c]pyrrol-4-ylidene]-2-methylpropane-2-sulfinamideHCID 87063931(NE,S)-N-[(3aS,6aR)-2-benzyl-1,3,3a,5,6,6a-hexahydrocyclopenta[c]pyrrol-4-ylidene]-2-methylpropane-2-sulfinamide

Reagents, catalysts & solvents 2

HCID 76524Titanium tetraethoxideCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
60 °C

Procedure

2-Benzylhexahydrocyclopenta[c]pyrrol-4(5H)-one (16.28 g, 76 mmol), titanium tetraethoxide (28.5 mL, 137 mmol), and (S)-2-methylpropane-2-sulfinamide (10.452 g, 86 mmol) were combined in tetrahydrofuran (200 mL). The reaction was heated at 60° C. overnight. The reaction was then reduced in volume to about half and poured into 150 mL of saturated aqueous ammonium chloride. The precipitate was collected by filtration and washed with ethyl acetate. The filtrate was poured into a separatory funnel and the organic layer was removed. The aqueous layer was extracted with ethyl acetate (3×100 mL). The organic washes were combined and washed with brine, dried (Na2SO4) and concentrated. The crude material was chromatographed using silica gel cartridge (Analogix®, Burlington, Wis., RS65-400) eluting with 5-100% ethyl acetate/hexanes to give (S,E)-N-((3aR,6aS)-2-benzylhexahydrocyclopenta[c]pyrrol-4(5H)-ylidene)-2-methylpropane-2-sulfinamide and (S,E)-N-((3aS,6aR)-2-benzylhexahydrocyclopenta[c]pyrrol-4(5H)-ylidene)-2-methylpropane-2-sulfinamide.

Workup

  1. filtrationThe precipitate was collected by filtration
  2. washwashed with ethyl acetate
  3. additionThe filtrate was poured into a separatory funnel
  4. customthe organic layer was removed
  5. extractionThe aqueous layer was extracted with ethyl acetate (3×100 mL)
  6. washwashed with brine
  7. dry with materialdried (Na2SO4)
  8. concentrationconcentrated
  9. customThe crude material was chromatographed
  10. washeluting with 5-100% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-a68b0152b409443f93ec79085428533d
Source dataset
uspto-grants-2014_04
Patent number
US08691865B2

Reaction notes

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