The preparation of pyrimidine-2-carboxylates and 2-pyrimidineacetates by alkoxycarbonylation of respectively 2-chloropyrimidine and 2-(chloromethyl) pyrimidine with carbon monoxide in the presence of palladium acetate and 1, 1′-bis (diphenylphosphino) ferrocene is described. The new process uses readily available starting materials and affords the corresponding esters in good yields.