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While several catalyst systems have been utilized in the hydroesterification or methoxycarbonylation of alkenes or equivalent substrates, these reactions are conventionally performed in autoclave reactor systems under high CO pressure (20 70 bar) and thermal heating (70 – 110 C). In this paper, the first methoxycarbonylation reactions performed in a microwave reactor fitted with a gas-addition accessory system are reported on and compared to the same reactions performed under conventional heating in an autoclave reactor. Thus 1-octene, styrene, allylbenzene, oand p-methoxyallylbenzene and β-methylstyrene were subjected to methoxycarbonylation over a palladium acetate–aluminum triflate catalyst system at 12 bar and 95 C. Results obtained indicated the methoxycarbonylation of these alkenes to be much faster under microwave conditions when compared to conventional heating and improvements in conversion ranged between 3 and 5% for the more reactive substrates (1-octene and styrene) and 6 – 20% for the allylbenzenes and β-methylstyrene.

Palladium catalyzed hydroesterification of substituted alkenes under microwave conditions