Intermolecular, Branch-Selective, and Redox-Neutral Cp*IrIII-Catalyzed Allylic C-H Amidation

Herein, we report the redox-neutral, intermolecular, and highly branch-selective amidation of allylic C-H bonds enabled by Cp*Ir-III catalysis. A variety of readily available carboxylic acids were converted into the corresponding dioxazolones and efficiently coupled with terminal and internal olefins in high yields and selectivities. Mechanistic investigations support the formation of a nucleophilic Ir-III-allyl intermediate rather than the direct insertion of an Ir-nitrenoid species into the allylic C-H bond.