Breaking Amides using Nickel Catalysis

Amides have been widely studied for decades, but their synthetic utility has remained limited in reactions that proceed with rupture of the amide C–N bond. Using Ni catalysis, we have found that amides can now be strategically employed in several important transformations: esterification, transamidation, Suzuki–Miyaura couplings, and Negishi couplings. These methodologies provide exciting new tools to build C–heteroatom and C–C bonds using an unconventional reactant (i.e., the amide), which is ideally suited for use in multi-step synthesis. It is expected that the area of amide C–N bond activation using nonprecious metals will continue to flourish and, in turn, will promote the growing use of amides as synthons in organic synthesis.