Photoinduced Trifluoromethylation of Arenes and Heteroarenes Catalyzed by High‐Valent Nickel Complexes

Abstract

Abstract We describe a series of air‐stable Ni III complexes supported by a simple, robust naphthyridine‐based ligand. Access to the high‐valent oxidation state is enabled by the CF 3 ligands on the nickel, while the naphthyridine exhibits either a monodentate or bidentate coordination mode that depends on the oxidation state and sterics, and enables facile aerobic oxidation of Ni II to Ni III . These Ni III complexes act as efficient catalysts for photoinduced C(sp 2 )−H bond trifluoromethylation reactions of (hetero)arenes using versatile synthetic protocols. This blue LED light‐mediated catalytic protocol proceeds via a radical pathway and demonstrates potential in the late‐stage functionalization of drug analogs.