Palladium-Catalyzed Enantioselective α-Alkenylation of Alkylamines with Vinyl Bromides and Triflates

Chiral allylic amines are not only structural motifs in biologically active molecules but also versatile synthons for a wide variety of other chiral amines. Herein, we report a chiral palladium complex-catalyzed asymmetric α-C–H alkenylation of N-arylimidoyl cyanide alkylamines of broad scope with respect to both alkylamines and vinyl bromides or triflates, which establishes a versatile and enantioselective route from primary amines to chiral allylic amines. We demonstrate that this reaction is applicable for the asymmetric synthesis of a diverse array of chiral amines, including chiral α,α-dialkyl amines with subtly different alkyl groups. In light of the ready availability of both coupling partners and catalysts, we anticipate that this reaction will find wide applications in asymmetric synthesis. Mechanistic studies revealed that, in addition to its inductive effect, the N-arylimidoyl cyanide group, via a C≡N···Pd coordination, played a critical role in facilitating the deprotonation of α-C–H bonds of alkylamines.