Nickel-Catalyzed Electrochemical C(sp )-C(sp ) Cross-Coupling Reactions of Benzyl Trifluoroborate and Organic Halides*.

Reported here is the redox neutral electrochemical C(sp )-C(sp ) cross-coupling reaction of bench-stable aryl halides or β-bromostyrene (electrophiles) and benzylic trifluoroborates (nucleophiles) using nonprecious, bench-stable NiCl ⋅glyme/polypyridine catalysts in an undivided cell configuration under ambient conditions. The broad reaction scope and good yields of the Ni-catalyzed electrochemical coupling reactions were confirmed by 50 examples of aryl/β-styrenyl chloride/bromide and benzylic trifluoroborates. Potential applications were demonstrated by electrosynthesis and late-stage functionalization of pharmaceuticals and natural amino acid modification, and three reactions were run on gram-scale in a flow-cell electrolyzer. The electrochemical C-C cross-coupling reactions proceed through an unconventional radical transmetalation mechanism. This method is highly productive and expected to find wide-spread applications in organic synthesis.