Li Mengna, Zhang Lei, Wu Benlai, Hong Maochun
College of Chemistry, Zhengzhou University, Zhengzhou 450001, P. R. China.
State Key Laboratory of Structural Chemistry, Fujian Institute of the Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Fujian, P. R. China.
Inorg Chem. 2024 Jan 8;63(1):381-389. doi: 10.1021/acs.inorgchem.3c03277. Epub 2023 Dec 27.
Mandelic acid and its analogues are highly valuable medical intermediates and play an important role in the pharmaceutical industry, biochemistry, and life sciences. Therefore, effective enantioselective recognition and separation of mandelic acid are of great significance. In this study, two of our recently reported chiral amine-alcohol-functionalized UiO-68-type Zr-HMOFs and with high chemical stability, abundant binding sites, and large chiral pores were selected as chiral selectors for the enantioselective separation of mandelic acid (MA), methyl mandelate (MM), and other chiral molecules containing only one phenyl. Materials and exhibited excellent enantioselective separation performance for MA and MM. Especially for the separation of racemate MA, the enantiomeric excess values reached 97.3 and 98.9%, which are the highest reported values so far. Experimental and density functional theory (DFT) computational results demonstrated that the introduction of additional phenyls on the chiral amine alcohol pendants in had somewhat impact on the enantioselective adsorption and separation of MA or MM compared with , but it was not significant. Further research on the enantioselective separation of those chiral adsorbates containing only one phenyl by material indicated the crucial role of the groups directly bonded to the chiral carbons of the adsorbates in the selective separation of enantiomers, especially showing higher enantioselectivity for the adsorbates with two hydrogen-bonding groups directly bonded to its chiral carbon.
扁桃酸及其类似物是极具价值的医药中间体，在制药工业、生物化学和生命科学中发挥着重要作用。因此，高效对映选择性识别和分离扁桃酸具有重要意义。在本研究中，我们选择了最近报道的两种具有高化学稳定性、丰富结合位点和大手性孔道的手性胺醇功能化UiO-68型锆基金属有机框架材料作为手性选择剂，用于对映选择性分离扁桃酸（MA）、扁桃酸甲酯（MM）和其他仅含一个苯基的手性分子。材料 和 对MA和MM表现出优异的对映选择性分离性能。特别是对于外消旋体MA的分离，对映体过量值分别达到97.3%和98.9%，这是迄今为止报道的最高值。实验和密度泛函理论（DFT）计算结果表明，与 相比， 在其手性胺醇侧链上引入额外苯基对MA或MM的对映选择性吸附和分离有一定影响，但不显著。对材料 对那些仅含一个苯基的手性吸附质的对映选择性分离的进一步研究表明，直接连接到吸附质手性碳上的基团在对映体的选择性分离中起着关键作用，特别是对于有两个氢键基团直接连接到其手性碳上的吸附质表现出更高的对映选择性。
