Nickel-Catalyzed Enantioconvergent Reductive Hydroalkylation of Unactivated Alkenes with α‑Pyridyl Alkyl Electrophiles

Methods for the synthesis of chiral organic compounds bearing pyridyl-substituted stereogenic centers are of great interest to agrochemical, pharmaceutical, and synthetic laboratories in their search for unique entities. Here, a concise and modular method for the enantioconvergent hydroalkylation of widely available alkenes to introduce stereogenic C­(sp³) centers has been established via a nickel/Box catalyst with α-pyridyl alkyl bromide. The mild reaction conditions enable a remarkably broad substrate scope and good functional-group tolerance, leading to the formation of a variety of enantioenriched alkylated pyridine derivatives in good yields with high enantioselectivities. Further application of enantioenriched pyridine derivatives is demonstrated by an asymmetric Si–H bond insertion, leveraging the productive utility of this modular strategy.