β,γ-Regioselective Inverse-Electron-Demand Aza-Diels-Alder Reactions with α,β-Unsaturated Aldehydes via Dienannine Catalysis

A stereoselective inverse-electron-demand aza-Diels-Alder cycloaddition process of cyclic 1-aza-1,3-butadienes and alpha,beta-unsaturated aldehydes has been developed via dienamine catalysis. This reaction exhibits excellent beta,gamma-regioselectivity for enal substrates with substantial structural diversity and broad functionalities, readily producing highly enantioenriched fused piperidine derivatives and enabling efficient sequential construction of complex polycyclic frameworks.