NiH-Catalyzed Reductive Relay Hydroalkylation: A Strategy for the Remote C(sp(3))-H Alkylation of Alkenes

The terminal-selective, remote C(sp(3))-H alkylation of alkenes was achieved by a relay process combining NiH-catalyzed hydrometalation, chain walking, and alkylation. This method enables the construction of unfunctionalized C(sp(3))-C(sp(3)) bonds under mild conditions from two simple feedstock chemicals, namely olefins and alkyl halides. The practical value of this transformation is further demonstrated by the large-scale and regioconvergent alkylation of isomeric mixtures of olefins at low catalyst loadings.