Abstract Diels-Alder reaction of thebaine with maleimides is structurally specific and yields [7, 8, 3′, 4′]-succinimido-endo-ethenotetrahydrothebaines containing N′-alkyl, cycloalkyl, aralkyl or aryl substituents. N′-[1 (S)-hydroxymethyl-2-methylpropyl]-succinimido- 6, 14-endo-ethenotetrahydrothebaine formed in reaction of S-valinol with (7α, 8α)-anhydrido- 6, 14-endo-ethenotetrahydrothebaine. The reduction of the adducts by LiAlH 4 afforded N ...