Oxidative carbonylation

Oxidative carbonylation is a class of reactions that use carbon monoxide in combination with an oxidant to generate esters and carbonate esters.

These transformations utilize transition metal complexes as homogeneous catalysts.

Oxidative carbonylation, using palladium-based catalysts, allows certain alkenes to be converted into homologated esters: Such reactions are assumed to proceed by the insertion of the alkene into the Pd(II)-CO2Me bond of a metallacarboxylic ester followed by beta-hydride elimination (Me = CH3).

[1] The conversion of methanol to dimethylcarbonate by oxidative carbonylation is economically competitive with phosgenation.

This reaction is practiced commercially using Cu(I) catalysts:[2] The preparation of dimethyl oxalate by oxidative carbonylation has also attracted commercial interest.