An efficient method for the first ene-reaction of 2-aryl-3H-indol-3-ones with allyltrimethylsilane has been developed for the first time. The reaction proceeded under the catalysis of Pd(OAc)2 and chiral phosphoric ligand L11 in the presence of Cu(CF3COO)2·XH2O, PivOH, and 5 Å molecular sieves in DMSO at 60 °C. The present methodology can avoid the impact of amine products generated by the reaction on the catalyst, and at the same time, the high catalytic activity of classical palladium catalysts still has catalytic ability for low electrophilic keto-imines. The desired products were furnished in excellent yields with good enantioselectivity.