General Olefin Synthesis by the Palladium‐Catalyzed Heck Reaction of Amides: Sterically Controlled Chemoselective NC Activation

Abstract

Metal-catalyzed reactions of amides proceeding via metal insertion into the N-CO bond are severely underdeveloped due to resonance stabilization of the amide bond. Herein we report the first Heck reaction of amides proceeding via highly chemoselective N-CO cleavage catalyzed by Pd(0) utilizing amide bond ground-state destabilization. Conceptually, this transformation provides access to a myriad of metal-catalyzed transformations of amides via metal insertion/decarbonylation.