The Heck Carbonylation: Palladium-Catalyzed Alkoxycarbonylation of Organic Halides

Keywords

carboalkoxylation - carbon monoxide - Heck carbonylation - palladium catalysis

Significance

Two years after the invention of the famous Heck reaction (J. Org. Chem. 1972, 37, 2320), Heck and co-workers reported the palladium-catalyzed alkoxycarbonylation of aryl, benzyl, and vinyl halides with an alcohol under a carbon monoxide atmosphere. This carbonylative coupling is broadly applicable and represents a pivotal transformation for the synthesis of esters.

Comment

Heck and co-workers proposed two possible mechanisms for the palladium-catalyzed alkoxycarbonylation (see scheme). The mixtures of alkene geometries observed in certain cases are likely due to a π-allylic palladium intermediate, which can lead to both Z and E products.

Publication History

Article published online:
20 December 2024