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Enantioseparation of fluorinated 3-arylthio-4,4’-bipyridines: Insights into chalcogen and π-hole bonds in high-performance liquid chromatography
Journal of Chromatography A ( IF 4.1 ) Pub Date : 2018-06-25 , DOI: 10.1016/j.chroma.2018.06.060
Paola Peluso , Carlo Gatti , Alessandro Dessì , Roberto Dallocchio , Robin Weiss , Emmanuel Aubert , Patrick Pale , Sergio Cossu , Victor Mamane

A chalcogen bond (ChB) is a σ-hole-based noncovalent interaction between a Lewis base and an electrophilic element of Group VI (O, S, Se, Te), which behaves as a Lewis acid. Recently, we demonstrated that halogen bond, the more familiar σ-hole-based interaction, is able to promote the enantioseparation of chiral compounds in HPLC environment. On this basis, an investigation to detect ChBs, functioning as stereoselective secondary interactions for HPLC enantioseparations, was started off and the results of this study are described herein. Our investigation also focused on the impact of the perfluorinated aromatic ring as a π-hole donor recognition site. For these purposes, seven atropisomeric fluorinated 3-arylthio-4,4’-bipyridines were designed, synthesized and used as potential ChB donors (ChBDs) with two cellulose-based chiral stationary phases (CSPs) containing carbonyl groups as ChB acceptors (ChBAs). In addition, one and two analogues lacking fluorine and sulphur, respectively, were prepared as terms of comparison. The design of the test analytes was computationally guided. In this regard, electrostatic potentials (EPs) associated with σ- and π-holes were computed and the atomic contributions to the sulphur EP maxima were derived using a molecular space partitioning in terms of Bader’s atomic basins. This procedure is akin to the Bader-Gatti electron density source function (SF) decomposition, yet suitably extended to the EP field. For five 3-substituted-4,4’-bipyridines, thermodynamic parameters were derived from van’t Hoff plots. Finally, the use of molecular dynamic (MD) simulation to model ChB in cellulose-analyte complexes was explored. Evidences that σ-hole and π-hole interactions can jointly drive HPLC enantioseparations through recognition sites generated by electronic charge depletion emerged from both experimental results and theoretical data.



中文翻译:

氟化3-芳硫基4,4'-联吡啶的对映体分离:高效液相色谱法中硫族元素和π孔键的发现

硫属元素键(ChB)是路易斯碱与第VI组(O,S,Se,Te)的亲电元素(起路易斯酸的作用)之间基于σ孔的非共价相互作用。最近,我们证明了卤素键(更熟悉的基于σ孔的相互作用)能够促进HPLC环境中手性化合物的对映体分离。在此基础上,开始了对检测ChBs的研究,该ChBs对HPLC对映体的分离具有立体选择性的次级相互作用,在此描述了该研究的结果。我们的研究还集中在全氟化芳环作为π孔供体识别位点的影响上。为了这些目的,设计了七个阻转异构的氟化3-芳硫基-4,4'-联吡啶,合成并用作潜在的ChB供体(ChBD),具有两个基于纤维素的手性固定相(CSP),其中含有羰基作为ChB受体(ChBA)。另外,分别制备了一种和两种缺乏氟和硫的类似物作为比较的条件。测试分析物的设计在计算上得到指导。在这方面,计算了与σ和π孔相关的静电势(EPs),并使用了基于Bader原子盆的分子空间划分方法,得出了对硫EP最大值的原子贡献。此过程类似于Bader-Gatti电子密度源函数(SF)分解,但适当地扩展到了EP领域。对于五个3-取代的4,4'-联吡啶,热力学参数来自van't Hoff图。最后,探索了使用分子动力学(MD)模拟在纤维素-分析物复合物中建立ChB的模型。实验结果和理论数据均显示出σ孔和π孔相互作用可以共同驱动HPLC对映体通过电荷耗尽产生的识别位点的证据。

更新日期:2018-06-25
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