Palladium‐Catalyzed Hydroesterification of Alkynes Employing Aryl Formates without the Use of External Carbon Monoxide

A highly efficient hydroesterification of alkynes employing aryl formates has been developed without the use of external carbon monoxide and at ambient pressure. The reaction in the presence of a palladium‐xantphos catalyst system selectively affords α,β‐unsaturated esters in good to high yields. Use of an aryl formate is crucial and alkyl formates did not react at all. The hydroesterification of norbornene and terminal alkenes also readily proceeded under similar reaction conditions. A mechanistic study showed that conversion of aryl formates to carbon monoxide and phenol derivatives occurred in the hydroesterification. Xantphos is highly effective as a ligand both in the conversion of aryl formates and the hydroesterification reactions.