Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.
WPI Nano Life Science Institute (WPI-NanoLSI), Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.
J Chromatogr A. 2020 Jul 5;1622:461173. doi: 10.1016/j.chroma.2020.461173. Epub 2020 May 3.
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 (-NH) groups, which was prepared by the polymerization of a phthalimide-protected diphenylacetylene monomer using WCl-PhSn 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.
具有光学活性酰苯胺侧基的聚二苯乙炔（聚-1）是通过光学活性羧酸与含有氨基（-NH）基团的关键前体聚合物的缩合反应合成的，该前体聚合物是通过使用 WCl-PhSn 作为催化剂聚合苯并咪唑保护的二苯乙炔单体，然后使用水合肼在所得聚合物中进行苯并咪唑脱保护来制备的。聚-1在 DMF 中热退火时形成了优先手性的螺旋构象（h-聚-1），因为侧基具有手性。聚-1 和 h-聚-1 作为高效液相色谱的手性固定相（CSP），表现出与具有相应光学活性酰胺侧基的类似聚二苯乙炔不同的手性识别能力。基于 h-聚-1 的 CSP 的拆分结果明显优于基于聚-1 的 CSP，这是由于优先手性的大分子螺旋性。在测试的外消旋体中，基于 h-聚-1 的 CSP 表现出更高的手性识别能力，特别是对联萘化合物和手性金属配合物。
