Dicationic SEGPHOS-Pd complex-catalyzed ketoester-ene reaction with silyl enol ether can be achieved to produce an ene product with a quaternary carbon center in high yield and enantioselectivity. Even lower catalyst loading (up to 0.01 mol%) can be performed without a significant decrease in yield and enantioselectivity; this will open doors to industrial applications of chiral Lewis acid catalysis.