A novel chiral ligand mimicking N-Ar axial chirality, (S)-N-[2-(diphenylphosphanyl)naphthalen-1-yl]-2-(piperidinylmethyl)piperidine, was found to exhibit good enantio selectivity (up to 80% ee) in the asymmetric cross-coupling reaction of 1-phenylethylmagnesium chloride with beta-bromostyrene derivatives. Additionally, this type ligand is appealing, because it allows the synthesis of a wide variety of analogues.