Synthesis of macropolycycles comprising diazacrown and adamantane moieties via Pd-catalyzed amination reaction

N,N’-bis(bromobenzyl) substituted diazacrown ethers were obtained in the reactions of corresponding free diazacrowns with two equivalents of bromobenzyl bromides in high yields. These compounds were introduced in the Pdcatalyzed amination reaction with 1,3-bis(aminomethyl) and 1,3-bis(2-aminoethyl)adamantanes to give macrobicyclic products. The yields were shown to be dependent on the nature of starting diazacrown derivatives and diamines. N,N’bis(3-bromobenzyl) substituted diazacrown ethers provided better yields of the target macrobicycles than N,N’-bis(4bromobenzyl) derivatives. In the latter case substantial amounts of cyclic oligomers were formed and isolated.