(R)-(-)-N,N-Dimethyl-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethylamine can be used as reactant/reagent in enantioselective palladium-catalyzed [3+2] cycloaddition of propargylic esters with β-ketoesters in presence of a chiral ferrocene/benzimidazole-based P,N-ligand.