Nickel-Catalyzed Csp2–Csp3 Cross-Coupling via C–O Bond Activation

A new and efficient nickel-catalyzed alkylation of CAr–O electrophiles with B-alkyl-9-BBNs is described. The transformation is characterized by its functional group tolerance and provides a practical and versatile access to various Csp2–Csp3 bonds through Csp2–O substitution, without the restriction of β-hydride elimination. Moreover, the advantage of the newly developed method was demonstrated in a selective and sequential C–O bond activation process.