Preparation of a 1,1'-Binaphthyl-based Chiral Polyimine Macrocycle Bonded Chiral Stationary Phase by Thiol-ene Click Reaction and Its Enantioseparation Performance in High-Performance Liquid Chromatography

Chiral macrocycles have emerged as attractive media for chromatographic enantioseparation due to their excellent host-guest recognition properties. In this study, a new chiral stationary phase (CSP) based on 1,1'-binaphthyl chiral polyimine macrocycle (CPM) was reported. The CPM was synthesized by one-step aldehyde-amine condensation of (S)-2,2'-dihydroxy-[1,1'-binaphthalene]-3,3'-dicarboxaldehyde with 1,2-phenylenediamine and bonded on thiolated silica via the thiol-ene click reaction to afford the CSP. The enantioseparation performance of the CSP was evaluated by separating different types of racemates including alcohols, esters, ketones, amides, organic acids, and ethers in both normal-phase (NP) and reversed-phase (RP) elution modes. As a result, enantioseparations of 10 and 15 racemates were achieved in the two elution modes, respectively. Meanwhile, the effects of chromatographic conditions on separation, such as mobile phase composition and injection mass, were studied in detail. Moreover, a comparison of the proposed CSP for the separation of the tested racemates with commercial Chiralcel OD-H and Chiralpak AD-H columns was also conducted, and results revealed that the proposed CSP can achieve some enantioseparations that cannot be achieved by the two commercial columns. This study indicates that the chiral macrocycle is a promising chiral selector for high-performance liquid chromatography.