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 Pd-catalyzed 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(4-bromobenzyl) derivatives. In the latter case substantial amounts of cyclic oligomers were formed and isolated.