[GRAPHICS] An effective chiral palladium catalyst [Pd(CH3CN)(2)(S)-Tol-BINAP](SbF6)(2) (2b) is developed for asymmetric glyoxylate-ene reactions. This palladium dicationic catalyst provides a simple but efficient approach to the asymmetric synthesis of alpha -hydroxy esters in excellent yields with high enantioselectivities at relatively higher reaction temperature (60 degreesC).