Palladium-Catalyzed Amination in the Synthesis of Polyazamacrocycles Containing a 1,3-Disubstituted Benzene Moiety

Abstract The synthesis of a new family of polyaza- and polyoxa­polyazamacrocycles by a simple and efficient one-pot palladium-catalyzed diamination of 1,3-dibromobenzene is described. The dependence of the nature of the starting polyamines on the yield of the products is demonstrated. The synthesis of N α ,N ω -bis(3-bromophenyl)-substituted polyamines is elaborated to obtain intermediates for the synthesis of polyazamacrocycles consisting of two polyamine and two benzene fragments (cyclodimers). The formation of tri- and tetraarylated polyamines is studied and regularities of the process are established. The synthesis of 1,3-bis(polyamino)-substituted benzenes is also described.