Dual C–F, C–H Functionalization via Photocatalysis: Access to Multifluorinated Biaryls

Multifluorinated biaryls are challenging to synthesize and yet are an important class of molecules. Because of the difficulty associated with selective fluorination, this class of molecules represent a formidable synthetic challenge. An alternative approach to selective fluorination of biaryls is to couple an arene that already possesses C–F bonds in the desired location. This strategy has been regularly utilized and relies heavily on traditional cross-coupling strategies that employ organometallics and halides (or pseudohalides) in order to achieve the coupling. Herein we report conditions for the photocatalytic coupling via direct functionalization of the C–F bond of a perfluoroarene and C–H bond of the other arene to provide an expedient route to multifluorinated biaryls. The mild conditions and good functional group tolerance enable a broad scope, including access to the anti-Minisci product of basic heterocycles. Finally, we demonstrate the value of the C–F functionalization approach by utilizing the high fluorine content to systematically build complex biaryls containing between two and five Caryl–F bonds via the synergistic use of photocatalysis and SNAr chemistry.