Acetonitrile → HCID 20694308, compound

HRID 380519Notes

Reaction equation

HRID 380519 reaction equation
C([N:4]1[CH2:8][C@@H:7]([C:9]2[CH:13]=[CH:12][S:11][CH:10]=2)[C@H:6]([CH2:14][N:15]2[CH2:20][CH2:19][CH:18]([C:21]3[CH:26]=[CH:25][C:24]([F:27])=[CH:23][CH:22]=3)[CH2:17][CH2:16]2)[CH2:5]1)C=C.CC#N>C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cl-].[Rh].O>[F:27][C:24]1[CH:25]=[CH:26][C:21]([CH:18]2[CH2:17][CH2:16][N:15]([CH2:14][C@H:6]3[C@H:7]([C:9]4[CH:13]=[CH:12][S:11][CH:10]=4)[CH2:8][NH:4][CH2:5]3)[CH2:20][CH2:19]2)=[CH:22][CH:23]=1

Participants

5

Reactant 2

HCID 6342AcetonitrileHCID 20694312HCID 20694312, compound

Product 1

HCID 20694308HCID 20694308, compound

Reagents, catalysts & solvents 2

HCID 84599Chlorotris(triphenylphosphine)rhodium(I)CatalystHCID 962WaterSolvent

Procedure

A mixture of 1.2 g (3.2 mmol) of 1-Allyl-3-(R)-(4-(4-fluorophenyl)piperidinylmethyl)-4-(R)-(3-thienyl)pyrrolidine and 0.19 g (0.2 mmol) of Wilkinson's catalyst ([Rh(PPh)3Cl] in 20 mL of an 85% solution of CH3CN in water in a flask fitted with a short path distillation head and an addition funnel for added solvent was heated to reflux. As solvent is azeotroped off, more is added to maintain the original concentration. After stirring at reflux for 4 h, the reaction mixture was concentrated. To the residue was added 3 mL of 2 N HCl and this mixture was partitioned between EtOAc and water. The aqueous fraction was washed with EtOAc and was then made basic with 2 N NaOH solution. The aqueous fraction was then extracted with EtOAc. The combined organic fractions were washed with sat'd NaCl solution, dried over MgSO4, filtered and the filtrate was concentrated to give the title compound which was used without further purification. Mass Spectrum (CI) m/e=345 (M+1)

Workup

  1. customfitted with a short path distillation head and an addition funnel
  2. additionfor added solvent
  3. temperaturewas heated to reflux
  4. customAs solvent is azeotroped off
  5. additionmore is added
  6. temperatureto maintain
  7. concentrationthe original concentration
  8. temperatureat reflux for 4 h
  9. concentrationthe reaction mixture was concentrated
  10. additionTo the residue was added 3 mL of 2 N HCl
  11. customthis mixture was partitioned between EtOAc and water
  12. washThe aqueous fraction was washed with EtOAc
  13. extractionThe aqueous fraction was then extracted with EtOAc
  14. washThe combined organic fractions were washed with sat'd NaCl solution
  15. dry with materialdried over MgSO4
  16. filtrationfiltered
  17. concentrationthe filtrate was concentrated

Sources & evidence

ORD record
ord-96d249dcc5084fd985c132c947d8ef92
Source dataset
uspto-grants-2001_10
Patent number
US06303593B1

Reaction notes

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