Distinguishing Competing Mechanistic Manifolds for C(acyl)-N Functionalization by a Ni/-Heterocyclic Carbene Catalyst System.

Carboxylic acid derivatives are appealing alternatives to organohalides as cross-coupling electrophiles for fine chemical synthesis due to their prevalence in biomass and bioactive small molecules as well as their ease of preparation and handling. Within this family, carboxamides comprise a versatile electrophile class for nickel-catalyzed coupling with carbon and heteroatom nucleophiles. However, even state-of-the-art C(acyl)-N functionalization and cross-coupling reactions typically require high catalyst loadings and specific substitution patterns.