1,1,2-Trisubstituted alkenes with a single strongly electronic withdrawing activator, which are unreactive electron-deficient alkenes in transition metal-catalyzed [3+2] cycloaddition with vinyl three-membered heterocycles, were used in the Pd-catalyzed asymmetric cycloaddition of vinyl epoxides, affording multifunctionalized tetrahydrofurans in high yields with high diastereo- and enantioselectivities.