Carraro Maria L, Palmeira Andreia, Tiritan Maria E, Fernandes Carla, Pinto Madalena M M
Laboratório de Química Orgânica, Departamento de Ciências Químicas, Faculdade de Farmácia, Porto, Portugal.
Interdisciplinary Centre of Marine and Environmental Research (CIIMAR), Edifício do Terminal de Cruzeiros do Porto de Leixões, Matosinhos, Portugal.
Chirality. 2017 Jun;29(6):247-256. doi: 10.1002/chir.22703. Epub 2017 Apr 25.
The enantioresolution and determination of the enantiomeric purity of 32 new xanthone derivatives, synthesized in enantiomerically pure form, were investigated on (S,S)-Whelk-O1 chiral stationary phase (CSP). Enantioselectivity and resolution (α and R ) with values ranging from 1.41-6.25 and from 1.29-17.20, respectively, were achieved. The elution was in polar organic mode with acetonitrile/methanol (50:50 v/v) as mobile phase and, generally, the (R)-enantiomer was the first to elute. The enantiomeric excess (ee) for all synthesized xanthone derivatives was higher than 99%. All the enantiomeric pairs were enantioseparated, even those without an aromatic moiety linked to the stereogenic center. Computational studies for molecular docking were carried out to perform a qualitative analysis of the enantioresolution and to explore the chiral recognition mechanisms. The in silico results were consistent with the chromatographic parameters and elution orders. The interactions between the CSP and the xanthone derivatives involved in the chromatographic enantioseparation were elucidated.
在（S,S）-Whelk-O1手性固定相（CSP）上研究了32种以对映体纯形式合成的新型氧杂蒽衍生物的对映体拆分及对映体纯度测定。实现了对映选择性和分离度（α和R），其值分别在1.41 - 6.25和1.29 - 17.20范围内。洗脱采用极性有机模式，以乙腈/甲醇（50:50 v/v）作为流动相，通常（R）-对映体先洗脱。所有合成的氧杂蒽衍生物的对映体过量（ee）高于99%。所有对映体对都实现了对映体分离，即使是那些与手性中心没有连接芳环部分的对映体对。进行了分子对接的计算研究，以对对映体拆分进行定性分析并探索手性识别机制。计算机模拟结果与色谱参数和洗脱顺序一致。阐明了CSP与参与色谱对映体分离的氧杂蒽衍生物之间的相互作用。
