<p>The Diels–Alder reaction is one of the most important reactions in organic synthesis, particularly when considering its ability to construct <i>sp</i>³-carbon-enriched carbocycles. Although extensive efforts have been dedicated to developing catalytic asymmetric variations of the Diels–Alder reaction, the generality of this textbook reaction is severely hindered by restrictive electronic requirements and substitution patterns. Here we disclose formal inverse-electron-demand [4+2] cycloadditions by transition metal catalysis. In these reactions, a single transition metal catalyst deploys two distinct processes, including generation and stabilization of transient electron-deficient dienes from Morita–Baylis–Hillman carbonates and promotion of subsequent [4+2] cycloadditions with external dienophiles. A wide range of <i>para</i>-substituted cyclohexenes are obtained in high yields with excellent chemo-, regio- and stereoselectivities by using 1,3-dienes as dienophiles via the catalysis of a Ni(0)–chiral monophosphine complex. This strategy is also extended to the Pd(0) catalysis, by which 1,3-enynes are compatible as dienophiles to afford chiral 1,4-cyclohexadienes with high enantioselectivities.</p><p></p>