Reaction of (+/-)-methyl 2-arylcyclohexenyl carbonate with tosyl amide in the presence of a catalytic amount of Pd 2 dba.CHCl 3 and (S)-BINAPO produced 2-arylcyclohexenyl tosyl amide with a high ee along with the starting material with a high ee. The reaction involved two processes, and (+)- and (-)-methyl 2-arylcyclohexenyl carbonate gave the same (π-allyl)palladium complex with a chiral ligand, which gave 2-arylcyclohexenyl tosyl amide with a high ee by enantioselective substitution. The intermediary (π-allyl)palladium complex was synthesized, and the results of X-ray crystallography are shown.