Copper-catalyzed amination in the synthesis of polyoxadiamine derivatives of aza- and diazacrown ethers

Cu(I)-Catalyzed amination of N-(iodobenzyl) substituted azacrown ethers with propane-1,3-diamine and several polyoxadiamines was investigated. In the case of diamine excess and the use of CuI/l-proline catalytic system in EtCN the formation of the compounds with one azacrown and one diamine moieties was observed. When taking the excess of N-(iodobenzyl) derivative of azacrown ether and CuI/2-(isobutyryl)cyclohexanone catalytic system in DMF, bis(azacrown) substituted oxadiamine could be obtained. Amination of N,N’-di(iodobenzyl) substituted diazacrown ether was studied under the same conditions. The comparison of Pd(0)- with Cu(I)-mediated amination reactions was done using N-(bromobenzyl) substituted azacrown ethers.