Isopropenyl acetate → Methyl [3-(2-oxopropyl)phenyl]acetate

HRID 916071Notes

Reaction equation

HRID 916071 reaction equation
C[O-].C([Sn+](CCCC)CCCC)CCC.[CH3:16][O:17][C:18](=[O:27])[CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[C:22](Br)[CH:21]=1.C([O:31][C:32]([CH3:34])=[CH2:33])(=O)C.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>C1(C)C=CC=CC=1.C(OCC)(=O)C.[F-].[K+].C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:16][O:17][C:18](=[O:27])[CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[C:22]([CH2:33][C:32](=[O:31])[CH3:34])[CH:21]=1

Participants

9

Reactant 4

HCID 7916Isopropenyl acetateHCID 80271Tri-o-tolylphosphineHCID 11746402Methyl 2-(3-bromophenyl)acetateHCID 11964040Methoxytri-n-butylstannane

Product 1

HCID 21035403Methyl [3-(2-oxopropyl)phenyl]acetateYield 94%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolventHCID 522689Potassium FluorideSolvent

Procedure

Tributyltin methoxide (28.3 ml, 98.0 mmol), methyl-(3-bromophenyl)acetate (Preparation 44) (15.0 g, 65.0 mmol), isopropenyl acetate (10.8 ml, 98.0 mmol), palladium(II)acetate (750 mg, 3.30 mmol) and tri-ortho-tolylphosphine (2.00 g, 6.5 mmol) were stirred together in toluene (75 ml) at 100° C. under nitrogen for 5 hours. After cooling the reaction was diluted with ethyl acetate (150 ml) and 4M aqueous potassium fluoride solution (90 ml) and stirred for 15 minutes. The mixture was filtered through arbocel and the organic phase separated and reduced in vacuo. The residue was purified by flash column chromatography silica gel eluting with a solvent gradient of diethyl ether:pentane (0:100 to 25:75, by volume) changing to dichloromethane to give the title compound as a pale yellow oil (12.6 g).

Workup

  1. temperatureAfter cooling the reaction
  2. filtrationThe mixture was filtered through arbocel
  3. customthe organic phase separated
  4. customThe residue was purified by flash column chromatography silica gel eluting with a solvent gradient of diethyl ether:pentane (0:100 to 25:75, by volume)

Sources & evidence

ORD record
ord-56ed7409f68245f09c9b2c9f47b26bd5
Source dataset
uspto-grants-2007_09
Patent number
US07268147B2

Reaction notes

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