Palladium‐Catalyzed Carbonylative Difunctionalization of Unactivated Alkenes Initiated by Unstabilized Enolates

Abstract This report describes the first example of palladium‐catalyzed carbonylative difunctionalization of unactivated alkenes initiated by enolate nucleophiles. The approach involves initiation by an unstabilized enolate nucleophile under an atmospheric pressure of CO and termination with a carbon electrophile. This process is compatible with a diverse range of electrophiles, including aryl, heteroaryl, and vinyl iodides to yield synthetically useful 1,5‐diketone products, which were demonstrated to be precursors for multi‐substituted pyridines. A Pd I ‐dimer complex with two bridging CO units was observed although its role in catalysis is not yet understood.