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

HRID 898490Notes

Reaction equation

HRID 898490 reaction equation
C[O-].C([Sn+](CCCC)CCCC)CCC.Br[C:17]1[CH:18]=[C:19]([CH2:23][C:24]([O:26][CH3:27])=[O:25])[CH:20]=[CH:21][CH:22]=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>[CH3:27][O:26][C:24](=[O:25])[CH2:23][C:19]1[CH:20]=[CH:21][CH:22]=[C:17]([CH2:33][C:32](=[O:31])[CH3:34])[CH:18]=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]acetate

Reagents, catalysts & solvents 4

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

Procedure

Tributyltin methoxide (28.3 ml, 98 mmol), methyl (3-bromophenyl)acetate (WO 95/27692, pg. 16, e.g. 5a) (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 (2.0 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 concentrated in vacuo. The residue was purified column chromatography on silica gel eluting with diethyl ether:pentane (0:100 to 25:75 and then changing to dichloromethane), to yield 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. concentrationconcentrated in vacuo
  5. customThe residue was purified column chromatography on silica gel eluting with diethyl ether:pentane (0:100 to 25:75

Sources & evidence

ORD record
ord-10a691ca20304f518b71afe79a1cc4ee
Source dataset
uspto-grants-2008_04
Patent number
US07351742B2

Reaction notes

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