Ni-catalyzed regioselective hydrobenzylation of alkenes to afford C(sp3)–C(sp3) bonds using BH3 as a reductant†

The nickel-catalyzed reductive olefin hydrocarbonation reaction is one of the powerful tools for the formation of C(sp³)–C bonds. However, the reductive coupling of alkenes with benzyl halides to afford alkyl–benzyl products has rarely been studied using the well-established Ni/SiH methods. Herein, we report a method of Ni-catalyzed regioselective hydrobenzylation of unactivated alkenes to afford anti-Markovnikov products using BH₃ as a reductant. This method exhibits good functional group tolerance, a wide scope and high regioselectivity. The mild conditions enable the coupling of terminal and internal alkenes with primary and secondary benzyl halides.