Triphenylphosphine → 2-methyl-4-(2,5-dimethylphenyl)-3,5,6,7-tetrahydro-s-indacen-1(2H)-one

HRID 271802Notes

Reaction equation

HRID 271802 reaction equation
Br[C:2]1[C:13]2[CH2:12][CH2:11][CH2:10][C:9]=2[CH:8]=[C:7]2[C:3]=1[CH2:4][CH:5]([CH3:15])[C:6]2=[O:14].[CH3:16][C:17]1[CH:22]=[CH:21][C:20]([CH3:23])=[CH:19][C:18]=1B(O)O.[OH-].[K+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>ClCCl.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O.C(COC)OC>[CH3:15][CH:5]1[CH2:4][C:3]2[C:7](=[CH:8][C:9]3[CH2:10][CH2:11][CH2:12][C:13]=3[C:2]=2[C:18]2[CH:19]=[C:20]([CH3:23])[CH:21]=[CH:22][C:17]=2[CH3:16])[C:6]1=[O:14]

Participants

9

Reactant 4

HCID 11776TriphenylphosphineHCID 14797Potassium HydroxideHCID 2734347(2,5-Dimethylphenyl)boronic acidHCID 235470494-Bromo-2-methyl-2,3,6,7-tetrahydro-s-indacen-1(5H)-one

Product 1

HCID 687458502-methyl-4-(2,5-dimethylphenyl)-3,5,6,7-tetrahydro-s-indacen-1(2H)-oneYield 77%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolvent2×HCID 6344DichloromethaneSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

A mixture containing 30.0 g (107.5 mmol)) of 4-bromo-2-methyl-3,5,6,7-tetrahydro-2H-s-indacen-1-one, 410 ml of dimethoxyethane, 21.0 g (135.8 mmol) of 2,5-dimethylphenyl boronic acid, 20.0 g (321 mmol) of potassium hydroxide and 72 ml of water was degassed and the flask atmosphere replaced with nitrogen. Stirring was initiated and 0.60 g (2.7 mmol) of palladium acetate and 2.4 g (9.1 mmol) of triphenylphosphine were added. The reaction mixture was stirred at 78° C. for 4 h. After cooling, the mixture was poured into water and the organic phase was separated. The aqueous phase was extracted two times with 200 ml of dichloromethane. The combined organic fractions were dried and solvents removed on a rotoevaporator giving 45 g of crude product. The crude product was dissolved in dichloromethane and filtered through a plug of silica gel to give 24 g of target compound as an oil after evaporation of the solvent (77% yield based on the indacen-1-one starting material).

Workup

  1. customwas degassed
  2. stirringThe reaction mixture was stirred at 78° C. for 4 h
  3. temperatureAfter cooling
  4. customthe organic phase was separated
  5. extractionThe aqueous phase was extracted two times with 200 ml of dichloromethane
  6. customThe combined organic fractions were dried
  7. customsolvents removed on a rotoevaporator
  8. customgiving 45 g of crude product
  9. filtrationfiltered through a plug of silica gel
  10. customto give 24 g of target compound as an oil
  11. customafter evaporation of the solvent (77% yield

Sources & evidence

ORD record
ord-7475ffa52237491d83ff3945523c1004
Source dataset
uspto-grants-2008_11
Patent number
US07452949B2

Reaction notes

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