Herein, we report a cobalt-catalyzed hydroarylation of maleimides followed by an annulation sequence for the synthesis of polycyclic azaheterocycles in one pot. The reaction proceeds under redox-neutral conditions and is compatible with various functional groups. Notably, the asprepared product exhibits potential photophysical properties.

We herein report an unprecedented pathway to access γ-lactams using acetonitrile analogues as coupling partners without oxidants, ligands, and Lewis acids. The reaction undergoes Rh-catalyzed C­(sp2)–H addition to carbon-bound nitriles with the aid of an amide traceless auxiliary followed by an annulation sequence, featuring a broad substrate scope, good functional group tolerance, and excellent chemo/stereoselectivity. Scale-up reactions and late-stage derivatizations highlight the potential synthetic utility of this methodology. A plausible mechanism is proposed based on mechanistic investigations.