Enantioselective Syntheses of α‐Silyl Amines via a Copper‐N‐Heterocyclic Carbene Catalyzed Nucleophilic Silicon Transfer to Imines

We developed an efficient and enantioselective method for the synthesis of chiral α-silyl amines. In the presence of a copper(I)-chiral monodentate N-heterocyclic carbene complex (5 mol %), smooth nucleophilic silicon transfer from Me2PhSiBpin (pin=pinacolato) to tosyl-protected aldimines affords the corresponding α-silyl amines in 77–93 % yields over 15 examples and satisfactory ee of 79–99 %. The asymmetric silylation of ketimines was also explored.