Copper-Catalyzed γ-Cyanation of Aza-Baylis–Hillman Adducts Using Trimethylsilyl Cyanide

Abstract

A copper-catalyzed γ-cyanation of aza-Baylis–Hillman adducts via iminium ion formation adjacent to benzylic tertiary amines has been developed using tert-butyl hydroperoxide (TBHP) as the external oxidant. The protocol involves in situ formation of 4π-conjugated iminium ion intermediates that undergo nucleophilic attack by cyanide to provide valuable γ-cyanated α,β-unsaturated amines.