Asymmetric Synthesis of α‐Chiral Allylic Silanes by Enantioconvergent γ‐Selective Copper(I)‐Catalyzed Allylic Silylation

Gamma way: Regio- and enantioselective allylic substitution with a silicon nucleophile generated by copper(I)-catalyzed Si-B bond activation provides direct access to α-chiral allylic silanes from linear acceptors. The enantioconvergent catalysis employing McQuade's six-membered N-heterocyclic-carbene-copper(I) catalyst is applicable to aryl- and alkyl-substituted allylic phosphates (see scheme).