Influence of the nature of alkyl substituents on the high-performance liquid chromatography enantioseparation and retention of new atropisomeric 1,1′-bibenzimidazole derivatives on amylose tris(3,5-dimethylphenylcarbamate) chiral stationary phase

Six new atropisomeric heteroarenes were synthesized by connecting two 2-alkylbenzimidazole fragments via N-N junction. They differ by the substituent nature (methyl, ethyl, propyl, butyl, pentyl and hexyl) of the aliphatic function. The novel atropisomeric compounds were used as chiral probes to study the chromatographic behavior of the amylose tris(3,5-dimethylphenyl carbamate) (Chiralpak AD-3) chiral stationary phase (CSP) under normal phase mode. The pivotal role of the length and flexibility of the 2,2'-alkyl groups on retention, enantioselectivity and enantiomer elution order was demonstrated by enantioselective HPLC analysis. Additional information on the chiral recognition mechanism was obtained from the evaluation of the correlated thermodynamic data. (C) 2014 Elsevier B.V. All rights reserved.