Synthesis of a poly(diphenylacetylene) bearing optically active anilide pendants and its application to a chiral stationary phase for high-performance liquid chromatography

Abstract

Poly(diphenylacetylene) having optically active anilide pendants (poly-1) were synthesized by the condensation reaction of an optically active carboxylic acid with a key precursor polymer containing amino (-NH2) groups, which was prepared by the polymerization of a phthalimide-protected diphenylacetylene monomer using WCl6-Ph4Sn as a catalyst, followed by phthalimide deprotection in the resulting polymer using hydrazine monohydrate. Poly-1 formed a preferred-handed helical conformation (h-poly-1) upon thermal annealing in DMF because of chirality of the pendant group. Poly-1 and h-poly-1 showed different chiral recognition abilities from the analogous poly(diphenylacetylene)s, having the corresponding optically active amide pendants, as chiral stationary phases (CSPs) for high-performance liquid chromatography. The resolution results with the h-poly-1-based CSP were much better than those with the poly-1-based CSP owing to the preferred-handed macromolecular helicity. Among the tested racemates, the h-poly-1-based CSP exhibited superior chiral recognition ability, especially toward binaphthyl compounds and chiral metal complexes.