Palladium-Catalyzed Vinylic Substitution Reactions. An Approach to (Aminoalkyl)phencyclidines

Article abstract of DOI:10.1021/jo00326a033

4-Iodophencyclidine (5) was reacted with various N-alkenylphthalimides in the presence of 1 mol percent palladium acetate, triethylamine, and tri-o-tolylphosphine in acetonitrile as solvent at 100 deg C to give good yields of (E)-4-(phthalimidoalkenyl)phencyclidines (9a-c).Catalytic hydrogenation of the olefins gave 12a-c, and cleavage of the phthalimido moiety gave the desired 4-(aminoalkyl)phencyclidines (2a-c) which were characterized as their mixed thioureas.Amine 2b was also synthesized by reduction of the palladium-catalyzed phencyclidine-acrylonitrile adduct.Reaction of acrolein ethylene ketal with 5 in the presence of palladium acetate did not give adduct 15 but rather gave isomerized ketene acetal 17 which underwent further reaction to 16a or hydrolyzed to 16b upon workup.Transesterification of 16 with methanol gave methyl ester 18 which was identical with the ester obtained by catalytic reduction of the palladium-catalyzed adduct of 5 and methyl acrylate, 19.LAH reduction of 19 gave a 4/1 mixture of alcohols 21 and 22.Mass spectra and 13C NMR spectra are presented for these phencyclidines.