β,γ-Regioselective inverse-electron-demand aza-Diels-Alder reactions with α,β-unsaturated aldehydes via dienamine catalysis.

Abstract

A stereoselective inverse-electron-demand aza-Diels-Alder cycloaddition process of cyclic 1-aza-1,3-butadienes and α,β-unsaturated aldehydes has been developed via dienamine catalysis. This reaction exhibits excellent β,γ-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.