NiH‐Catalyzed Remote Asymmetric Hydroalkylation of Alkenes with Racemic α‐Bromo Amides

Reported here is a terminal‐selective, remote asymmetric hydroalkylation of olefins with racemic α‐bromo amides. The reaction proceeds by NiH‐catalyzed alkene isomerization and subsequent alkylation reaction, and can enantioconvergently introduce an unsymmetrical secondary alkyl group from a racemic α‐bromo amide onto a terminal C(sp 3 )−H position along the hydrocarbon chain of the alkene. This mild process affords a range of structurally diverse chiral α‐alkylalkanoic amides in excellent yields, and high regio‐ and enantioselectivities. In addition, the synthetic utility of this protocol is further highlighted by the regioconvergent conversion of industrial raw materials of isomeric olefin mixtures into enantioriched α‐alkylalkanoic amides on large scale.