Site-Selective Ni-Catalyzed Reductive Coupling of alpha-Haloboranes with Unactivated Olefins

A mild, chemo- and site-selective catalytic protocol that allows for incorporating an alkylboron fragment into unactivated olefins is described. The use of internal olefins enables C–C bond-formation at remote sp³ C–H sites, constituting a complementary and conceptually different approach to existing borylation techniques that are currently available at sp³ centers.