CpCo()-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- c ]imidazoles were readily accessed via 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. Cobalt( iii )-catalyzed thiocarbamate directed aminocarbonylation and amination of C-H bonds are described to access diverse amides.