Versatile Cp*Co(III)(LX) Catalyst System for Selective Intramolecular C–H Amidation Reactions

Herein, we report the development of a tailored cobalt catalyst system of Cp*Co­(III)­(LX) toward intramolecular C–H nitrene insertion of azidoformates to afford cyclic carbamates. The cobalt complexes were easy to prepare and bench-stable, thus offering a convenient reaction protocol. The catalytic reactivity was significantly improved by the electronic tuning of the bidentate LX ligands, and the observed regioselectivity was rationalized by the conformational analysis and DFT calculations of the transition states. The superior performance of the newly developed cobalt catalyst system could be broadly applied to both C­(sp²)–H and C­(sp³)–H carbamation reactions under mild conditions.