An umpolung strategy for chemically selective intermolecular cross-enolate-type coupling of N -alkenoxypyridinium salts with aldehydes.

An efficient method for the synthesis of 1,4-ketoaldehydes via the cross-coupling of N -alkenoxyheteroarenium salts and primary aldehydes is developed. This method provides a broad substrate scope and excellent functional group compatibility. The utility of this method is demonstrated via the diverse transformations of heterocyclic compounds and cycloheptanone, as well as the late-stage functionalization of biorelevant molecules.