Heterogeneous Bifunctional Catalytic, Chemo‐, Regio‐ and Enantioselective Cascade Inverse Electron Demand Diels–Alder Reaction

We present a bifunctional catalytic, chemo‐, regio‐ and enantioselective inverse electron demand Diels–Alder reaction (IEDDAR) cascade of a variety of methylenebut‐3‐enoates with azlactones at high levels of yield and enantioselectivity (up to 99% yield, and >99% ee) via a dual HOMOdienophiles and LUMOdienes activated pathway using a heterogeneous catalytic system. Meanwhile, a novel MNPs‐supported chiral thiourea was developed for economical and environment‐friendly purposes. The catalyst can be conveniently recycled and reused for 10 runs with only a slight loss of yield and enantioselectivity.