Dimethyl Sulfoxide → HCID 90961605, compound

HRID 1784348Notes

Reaction equation

HRID 1784348 reaction equation
Br[C:2]1[CH:3]=C[C:5]2[O:11][CH2:10][C@@H]3CCCN3[C:7](=O)[C:6]=2[CH:16]=1.[CH2:17]([N:19]([CH2:22][CH3:23])[CH2:20][CH3:21])[CH3:18].[CH3:24][OH:25].[OH2:26].CS(C)=[O:29]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH2:21]1[C@H:20]2[CH2:24][O:25][C:3]3[CH:2]=[CH:16][C:6]([C:5]([O:11][CH3:10])=[O:29])=[CH:7][C:23]=3[C:22](=[O:26])[N:19]2[CH2:17][CH2:18]1

Participants

8

Reactant 5

HCID 679Dimethyl SulfoxideHCID 887MethanolHCID 962WaterHCID 8471TriethylamineHCID 69063359HCID 69063359, compound

Product 1

HCID 90961605HCID 90961605, compound

Reagents, catalysts & solvents 2

HCID 812191,3-Bis(diphenylphosphino)propaneCatalyst2×HCID 167845palladium(II) acetateCatalyst2×

Conditions

Temperature
100 °C

Procedure

To a solution of (S)-7-Bromo-2,3,11,11a-tetrahydro-1H,5H-pyrrolo[2,1-c][1,4]-benzoxazepine-5-one (5 g; 17.76 mmol), prepared as described in Example 3J, in dimethylsulfoxide (80 ml) was added palladium acetate (225 mg; 1 mmol), 1,3-bis-(diphenylphosphino)propane (413 mg; 1 mmol), triethylamine (5 ml; 36 mmol) and methanol (4 ml). After stirring under argon until all solids had dissolved the reaction vessel was purged several times with carbon monoxide and placed under an atmosphere of carbon monoxide (balloon). The mixture was then heated to 100° C. and stirred overnight. Further portions of palladium acetate (0.50 mmol) and 1,3-bis-(diphenylphosphino)propane (0.50 mmol) were added and the mixture stirred at 100° C. for a further 6 h. After cooling water (200 ml) was added and the aqueous solution was extracted with three 75 ml portions of ethyl acetate. The combined extracts were dried (Na2SO4) and solvent evaporated under reduced pressure. The resulting brown oil was purified by column chromatography eluting with ethyl acetate. Further purification by recrystallisation from diethyl ether gave methyl (S)-2,3,11,11a-tetrahydro-1H,5H-pyrrolo[2,1-c][1,4]benzoxazepine-5-one-7-carboxylate (3.13 g) as a white crystalline solid

Workup

  1. dissolutionhad dissolved the reaction vessel
  2. customwas purged several times with carbon monoxide
  3. stirringstirred overnight
  4. stirringthe mixture stirred at 100° C. for a further 6 h
  5. additionwas added
  6. extractionthe aqueous solution was extracted with three 75 ml portions of ethyl acetate
  7. dry with materialThe combined extracts were dried (Na2SO4) and solvent
  8. customevaporated under reduced pressure
  9. customThe resulting brown oil was purified by column chromatography
  10. washeluting with ethyl acetate
  11. customFurther purification
  12. customby recrystallisation from diethyl ether

Sources & evidence

ORD record
ord-c8dbc932f36e4d468cc1d5184fcf87ba
Source dataset
uspto-grants-2009_03
Patent number
US07504390B2

Reaction notes

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