Synthesis of Trimacrocyclic Compounds Comprising Diazacrown Ether Moieties via Pd(0)-Catalyzed Amination Reactions

Macrobicycles comprising a central diazacrown structural unit were modified with two 3-bromobenzyl substituents and the resulting compounds were introduced in Pd(0)-catalyzed macrocyclization reactions with trioxadiamine, to give cryptand-like macrotricycles. In the second approach, diazacrown ethers were substituted with two 3,5-dibromobenzyl groups and their Pd(0)-catalyzed double macrocyclization with a series of oxadiamines produced a new family of trimacrocyclic compounds; the Pd(dba)2/RuPhos catalytic system was found to be the most efficient. The decoration of one trimacrocycle with four dansyl fluorophore groups produced a fluorescent molecular probe for Cu(II) and Al(III) cations. Keywords: Amination, cryptands, diazacrown ethers, macrocycles, Pd catalysis, polyamines.