[en] The ortho-palladization of R(+)-N-isopropyl-α-(2-naphthyl)ethylamine was realized under the conditions of the Cope-Friedrich reaction at an elevated temperature (64⁰C) compared with the normal temperature for the palladization of tertiary amines. It was established that the ortho-palladization of α-(2-naphthyl)ethylamines unsymmetrically substituted at the nitrogen atom is highly stereoselective and results in the fixation of the coordinated nitrogen atom of these ligands in only one of the two possible absolute configurations. On the basis of a comparative analysis of the chiral-optical and NMR characteristics of the obtained and of the previously investigated ortho-palladized compounds it was concluded that the nitrogen atom of the metallated ligand has the S/sup N/-configuration, determined by the R/sup C/-configuration of the adjacent asymmetric carbon center