A remote C(sp3 )-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.
Keywords: Asymmetric Synthesis; Bimetallic Catalysis; Chain-Walking; Protoboration; Unactivated Alkenes.
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