Optically active macrocyclic hexaazapyridinophanes decorated at the periphery: synthesis and applications in the NMR enantiodiscrimination of carboxylic acids

Abstract

A family of pyridine based dialdehydes has been efficiently prepared starting from chelidamic acid by chemical modification of its 4-hydroxyl group. The condensation of these dialdehydes with commercially available (1R,2R)-(−)-cyclohexane-1,2-diamine in the presence of Ba2+ template led, after the in situ reduction, to the synthesis of a family of enantiopure hexaazapyridinophanes substituted at the periphery. These new receptors have been used as chiral shift agents towards different carboxylic acids. Good splitting of the carboxylic acid NMR signals (up to ΔΔδ=0.13 ppm) were observed using substoichiometrical amount of the receptor.