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

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 CF₃ 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(sp² )-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.

Keywords: C−H bond functionalization; nickel; photoreactivity; radical formation; trifluoromethylation.