Synthesis and characterization of pyridine-based polyamido-polyester optically active macrocycles and enantiomeric recognition for D- and L-amino acid methyl ester hydrochloride.

H Zhao, W Hua

Index: J. Org. Chem. 65(10) , 2933-8, (2000)

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Abstract

Five new chiral macrocycles, 3a-e, have been prepared by the acylation cyclization of chiral diamine dihydrobromide intermediates 2a-c with 2,6-pyridinedicarbonyl dichloride in highly diluted solution at room temperature. The chiral diesters 1a-c needed for the preparation of the macrocycles were obtained from condensation of corresponding N-(Z)-L-amino acids and 2,6-bishydroxymethyl pyridine in the presence of DCC and DMAP. The enantiomeric recognition of chiral macrocycles 3a-e for D- and L-amino acid methyl ester hydrochlorides has been characterized by fluorescence spectra, which indicate that some of them exhibited significant chiral recognition for the enantiomers of D- and L-amino acid methyl ester hydrochlorides. The stoichiometry and binding constants of 3a-L-Am(2) and 3c-L-Am(2) complexes have been determined. An X-ray analysis of the chiral macrocycle 3b show that the chiral ligand is rather rigid and strained.