PdH-Catalyzed Electrooxidative Hydrofluorination of Aryl-Substituted Alkenes with Nucleophilic Fluorine Source

Transition metal-catalyzed hydrofluorination of alkenes has been extensively explored as a straightforward strategy to access aliphatic fluorides, but relies on the use of electrophilic fluorinating (F+) reagents. Herein we report an electrocatalytic approach for the hydrofluorination of aryl-substituted alkenes with nucleophilic fluorine (F-) source. The merger of palladium hydride catalysis with electrooxidation enables the transformation of styrenes and α,β-unsaturated carbonyl derivatives to the corresponding benzylic fluorides generally with high reaction efficiency. This method can also be applied to the late-stage derivatization of complex molecules containing pharmaceutically relevant moieties. Mechanistic studies suggest that the generation of a high-valent organopalladium intermediate via anodic oxidation is a crucial step in this reaction.