NHC‐Catalyzed Remote <i>γ,δ</i> –Protonation and Formal [3+3] Annulation to Access Functionalized Dihydropyridinones

Abstract We have developed an N ‐heterocyclic carbene (NHC)‐catalyzed [3+3] annulation of α,β−γ,δ‐unsaturated aldehydes with enamines for the asymmetric synthesis of dihydropyridinone that bearing an all‐carbon quaternary center. This strategy proceeding via the NHC‐mediated γ,δ–protonation of α,β−γ,δ−unsaturated aldehydes, followed by an asymmetric [3+3] cycloadditions. This protocol delivers a wide range of substituited dihydropyridinones in good yields with excellent enantioselectivities.