Palladium-Catalyzed Unimolecular Fragment Coupling of N-Allylamides via Elimination of Isocyanate

Transition metal-catalyzed unimolecular fragment coupling (UFC) is defined as processes that forge new chemical bonds through the extrusion of molecules, such as CO and CO₂, and the subsequent recombination of the remaining fragments. Herein, we report on a new UFC reaction that involves the palladium-catalyzed elimination of an isocyanate fragment from an amide, with the formation of carbon-carbon and carbon-heteroatom bonds. An organometallic intermediate that is relevant to the catalytic reaction was characterized by X-ray crystallography. This UFC reaction enables the late-stage transformation of an amide functionality, allowing amides to be used as a convertible directing or protecting group.