Abstract This paper reports the synthesis of various 5-halopyrimidine-4-carboxylic acid esters via the Minisci homolytic alkoxycarbonylation of 5-halopyrimidines. The reaction was found to be highly regioselective, allowing the one-step synthesis of useful amounts (> 10 g) of ethyl 5-bromopyrimidine-4-carboxylate where other methods proved difficult. Ethyl 5- bromopyrimidine-4-carboxylate was used for the preparation of potent CK2 inhibitors ...