Anthranil: An Aminating Reagent Leading to Bifunctionality for Both C(sp3)-H and C(sp2)-H under Rhodium(III) Catalysis

Previous direct C-H nitrogenation suffered from simple amidation/amination with limited atom-economy and is mostly limited to C(sp(2))-H substrates. In this work, anthranil was designed as a novel bifunctional aminating reagent for both C(sp(2)) H and C(sp(3)) H bonds under rhodium(III) catalysis, thus affording a nucleophilic aniline tethered to an electrophilic carbonyl. A tridendate rhodium(III) complex has been isolated as the resting state of the catalyst, and DFT studies established the intermediacy of a nitrene species.