Chiral perfluoroalkyl- and tris(perfluoroalkyl)silyl-derivatized analogues of the ligand MOP, having a fluorine content of 55.65 and 56.88%, respectively, have been prepared starting from optically active 6,6'-dibromo-2,2'-diethoxy-1,1'-binaphthyl. These ligands have been used in the palladium-catalyzed asymmetric substitution of 1,3-diphenylprop-2-enyl acetate with dimethyl malonate affording chiral products with e.e. of up to 37%.