Unlocking Photoredox/Nickel-Catalyzed Dehydrogenative Coupling of Alcohols and Aryl Halides to Access Aryl Ketones

The pursuit of diversity-oriented transformations from readily available feedstock chemicals plays a pivotal role in synthetic chemistry. In this context, the ultimate goal is the precise manipulation of reaction pathways through minimal modulation of reaction parameters, though challenging but highly desirable. Herein, we accomplished a visible-light-induced nickel-catalyzed dehydrogenative cross-coupling of aryl bromide with aliphatic alcohol, leading to the assembly of a range of structurally diverse aryl alkyl ketones. In contrast to the previously identified reaction manifolds (C–O coupling and α-C–OH arylation), this protocol realizes an uncharted cross coupling to simultaneously forge one C–C bond and one C═O bond formation via well-defined consecutive HAT processes, in which the basicity and solvent in the nickel-photoreaction system are crucial for manipulating the reaction sequence. The wide substrate scope, mild reaction conditions, and late-stage modification of structurally complex molecules comprehensively demonstrated the synthetic utilities of this transformation. Mechanistic studies shed light on the plausible reaction mechanism and the origin of the reactivity switch.