Mechanistic insights on C(acyl)-N functionalisation mediated by late transition metals.

The carboxamide functional group has a privileged role in organic and biological chemistry due to its prevalence and utility across synthetic and natural products. Due to n → π* delocalisation, amides and related functional groups are typically kinetically resistant to degradation. Nonetheless, over the past decade, transition metal catalysis has transformed our ability to utilise molecules featuring C(acyl)-N units as reactants. Alongside the burgeoning catalytic applications ranging from CO utilisation to small molecule synthesis, elucidation of the underlying mechanisms remains a critical ongoing effort. Herein, we aggregate and analyse current understanding of the mechanisms for C(acyl)-N functionalisation of amides and related functional groups with a focus on recent developments involving mechanisms unique to the late transition metals. Discussion is organized around three general mechanistic manifolds: redox-neutral mechanisms, 2e redox-cycling mechanisms, and mechanisms involving 1e redox steps. For each class, we focus on reactions that directly involve a transition metal mediator/catalyst in the C(acyl)-N cleavage step. We conclude with an outlook on the outstanding ambiguities and opportunities for innovation.