Abstract The synthesis of alkyl 2-chloro-3-formylacrylates 1 from alkyl pyruvates was carried out using Vilsmeier reaction. The reaction is highly stereoselective and leads to a 95: 5 mixture of Z and E stereoisomers. Both stereoisomers were characterized by 1 H and 13 C NMR. In CDCl 3 solution, the NMR data, particularly the NOEDIFF experiments, show that the major species formed is the Z stereoisomer. Heating compound 1 in THF at reflux ...