Abstract 1‐Aryl‐2(1H)pyrimidinones I reacted with α‐haloesters in the presence of zinc to give mainly 3,4‐dihydro‐4‐alkoxycarbonylmethyl‐1‐aryl‐2(1H)pyrimidinones IV in addition to the minor products of 3,6‐dihydro‐6‐alkoxycarbonylmethyl‐1‐aryl‐2(1H)pyrimidinones V. Further, 3,4‐dihydro derivatives IVa‐c were successfully converted into the corresponding exomethylene compounds Vla‐c in high yields.