Cross-coupling of amides by N–C activation

Development of new strategies encompassing activation of inert bonds has revolutionized organic synthesis. Transition-metal-catalyzed coupling of amide N–C bonds holds an enormous potential for widespread practical applications. In this lecture, recent developments in the selective activation of amide bonds by ground-state-destabilization-controlled metal insertion into the amide double bond will be presented. These reactions are enabled by virtue of decreased amidic resonance, which is a recurring theme of this new cross-coupling manifold. The selectivity in amide bond cross-coupling will be described. Representative examples to be discussed include Pd-, Ni- and Rh-catalyzed acyl- and aryl-decarbonylative cross-couplings.