Ligand Controlled Ir-Catalyzed Regiodivergent Oxyamination of Unactivated Alkenes

An intramolecular Ir­(III)-catalyzed regiodivergent oxyamination of unactivated alkenes provides valuable γ-lactams, γ-lactones and δ-lactams. The regioselectivity is controlled by the electronically tunable cyclopentadienyl Ir­(III)-complexes enabling oxyamination via either 5-exo or 6-endo pathways. With respect to the mechanism, we propose a highly reactive [3.1.0] bicycle intermediate derived from Ir­(V) nitrene-mediated aziridination to be a key intermediate toward the synthesis of γ-lactams.