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.