Enantio‐ and Regioconvergent Nickel‐Catalyzed C(sp(3))−C(sp(3)) Cross‐Coupling of Allylic Electrophiles Steered by a Silyl Group

A two‐step sequence for the enantio‐ and diastereoselective synthesis of exclusively alkyl‐substituted acyclic allylic systems with a stereocenter in the allylic position is reported. The asymmetric induction and the site selectivity are controlled in an enantio‐ and regioconvergent nickel‐catalyzed C(sp(3))−C(sp(3)) cross‐coupling of regioisomeric mixtures of racemic α‐/γ‐silylated allylic halides and primary alkylzinc reagents. The silyl group steers the allylic displacement towards the formation of the vinylsilane regioisomer, and the resulting C(sp(2))−Si bond serves as a linchpin for the installation of various C(sp(3)) substituents in a subsequent step.