Palladium(0)-Catalyzed Asymmetric Cross Inverse-Electron-Demand Diels–Alder Reaction between Distinct Electron-Deficient Dienes

Here we present an asymmetric and regioselective cross inverse-electron-demand Diels-Alder reaction between 2,4-dienyl carbonyls and 1-heterodienes or allylidenemalononitriles, by reversing the reactivity of the former electrophilic partners via <i>γ,δ</i>-dihapto coordination with palladium(0) and backdonation. A broad spectrum of multifunctional tetrahydropyridines, dihydropyrans and cyclohexene derivatives are generally constructed in high yields, diastereo- and enantioselectivity, even with low catalyst loadings (0.6 mol % of Pd).