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Pd-catalyzed amination reactions were employed for the synthesis of macrobicyclic compounds possessing cyclen or cyclam moieties, naphthylmethyl spacers and polyamine linkers. The results of the macrocyclization reactions involving 1,7-bis(4-bromonaphthyl-1-methyl)cyclen and 1,8-bis(4-bromonaphthyl-1-methyl)cyclam were shown to be dependent on the nature of starting tetraazamacrocycles and polyamines, the better yields being observed in the case of cyclen derivatives. Valuable macrotricyclic compounds were obtained as the second products in the reactions of 1,7-bis(4bromonaphthyl-1-methyl)cyclen with the majority of polyamines.

Pd-Сatalyzed Amination for the Synthesis of Macropolycycles Comprising Cyclen, Cyclam and Naphthalene Moieties