A highly enantioselective Friedel鈭扖rafts reaction catalyzed by a chiral phosphoric acid was developed. N-Boc-protected ethyl trifluoropyruvate imine was activated by 6 mol % of catalyst and reacted with a wide variety of indole derivatives to afford quaternary 伪-amino acids in excellent yields (up to 99%) and high enantioselectivities (up to 98:2 er).