Remote Site-Selective Asymmetric Protoboration of Unactivated Alkenes Enabled by Bimetallic Relay Catalysis.

A remote C(sp 3 )-H bond asymmetric borylation of unactivated alkenes was achieved by bimetallic relay catalysis. The reaction proceeded through reversible and consecutive β-H elimination/olefin insertion promoted by CoH species generated in situ, followed by copper-catalyzed asymmetric protoboration. The use of this synergistic Co/Cu catalysis protocol allowed the enantioselective protoboration of various unactivated terminal alkenes and internal alkenes, as well as an unrefined mixture of olefin isomers, at the distal less-reactive β-position to a functional group, leading to chiral organoboronates.