A new-type chiral ligand, (S)-N-[2-(diphenylphosphino)naphthyl]-2-(pyrrolidinylmethyl)pipeiidine mimicking N-Ar axial chirality, has been developed. This chiral ligand was found to exhibit 99% ee, with the use of (E)-1,3-diphenyl-2-propenyl acetate as the standard substrate, and achieved slightly better results than the Pfaltz and Trost ligands with the use of (E)-1-phenyl-3-trimethylsilyl-2-propenyl acetate as the substrate, in the palladium-catalyzed asymmetric allylic substitution. (C) 2002 Elsevier Science Ltd. All rights reserved.