Control of Vicinal Stereocenters through Nickel‐Catalyzed Alkyl–Alkyl Cross‐Coupling

Abstract Vicinal stereocenters are found in many natural and unnatural compounds. Although metal‐catalyzed cross‐coupling reactions of unactivated alkyl electrophiles are emerging as a powerful tool in organic synthesis, there have been virtually no reports of processes that generate, much less control, vicinal stereocenters. In this investigation, we establish that a chiral nickel catalyst can mediate doubly stereoconvergent alkyl–alkyl cross‐coupling, specifically, reactions of a racemic pyrrolidine‐derived nucleophile with cyclic alkyl halides (as mixtures of stereoisomers) to produce vicinal stereocenters with very good stereoselectivity.