Strategy for the Synthesis of Unsymmetrical N-Substituted Polyazamacrocycles.

摘要

Polyammonium macrocycles specifically designed for the complexation of anions have been found to form high affinity supramolecular complexes that, in some cases, lead to unique chemical transformations. Catalysis within the supramolecular complex has been particularly useful in exploring phosphoryl transfer reactions and in modeling enzymatic reactions that catalyze such reactions. In an effort to explore the effect of additional catalytic sites on polyammonium macrocycles the synthesis of a series of symmetrically substituted 24-membered hexaazamacrocycles containing pendant functionality was recently described. This report describes a facile approach found to be useful in the preparation of unsymmetrically N-substituted polyazamacrocycles. A convergent route is described for the preparation of unsymmetrical N-substituted polyammonium macrocycles that is potentially applicable for the synthesis of a wide variety of macrocycles of differing ring size and heteroatom substitution. (aw)