Synthesis of macrocycles containing two pyridine and two polyamine moieties via Pd-catalyzed amination

The synthesis of macrocycles containing two pyridine and two polyamine fragments was carried out by the Pd-catalyzed amination of 2,6-dihalopyridines using polyamines and dioxadiamine. Two alternative approaches were elaborated and compared: via intermediate formation of Nα,Nω-bis(6-halopyridin-2-yl)polyamines or via 2,6-bis(polyamino)substituted pyridines. The yields of linear and cyclic products were shown to be strongly dependent on the nature of the starting polyamines and that of the halogen atom.