Cp*Co(III)-catalyzed thiocarbamate-directed C-H aminocarbonylation, amination, and cascade annulation of pyrroles.

Cobalt(III)-catalyzed thiocarbamate directed aminocarbonylation and amination of C-H bonds are described to access diverse amides. Biologically relevant pyrrolo[1,2-]imidazoles were readily accessed one-pot intramolecular cyclization at the thiocarbamoyl directing group. Notably, C-N amidation proceeded smoothly with an elusive catalyst TON of 250 for this Cp*Co(III)-catalysis. Broad scope, scalability, and easy removal of DG are other key features of these methods. The mechanisms of these C-H amidation reactions were proposed through control experiments and DFT calculations.