有机化学 ›› 2015, Vol. 35 ›› Issue (7): 1531-1536.DOI: 10.6023/cjoc201502018 上一篇    下一篇

研究简报

杯[4]脯氨酸衍生物的合成及其对扁桃酸对映异构体的手性识别

李正义a, 周坤a, 来源a, 孙小强a, 王乐勇b   

  1. a 常州大学石油化工学院 江苏省绿色催化材料与技术重点实验室 常州 213164;
    b 超分子化学与智能材料实验室 南京大学化学化工学院 南京 210093
  • 收稿日期:2015-02-10 修回日期:2015-03-02 出版日期:2015-07-25 发布日期:2015-03-19
  • 通讯作者: 孙小强, 王乐勇 E-mail:sunxiaoqiang@yahoo.com,Lywang@nju.edu.cn
  • 基金资助:

    国家自然科学基金(No. 21002009)、江苏省高校自然科学研究重大项目(Nos. 12KJA150002, 14KJA150002)、江苏省优势学科和江苏省青蓝工程资助项目

Synthesis of Calix[4]proline Derivatives and Their Chiral Recognition for Enantiomers of Mandelic Acid

Li Zhengyia, Zhou Kuna, Lai Yuana, Sun Xiaoqianga, Wang Leyongb   

  1. a Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, School of Petrochemical Engineering, Changzhou University, Changzhou 213164;
    b Laboratory for Supramolecular Chemistry and Dynamic Materials, School of Chemistry and Chemical Engineering, Nanjing Universty, Nanjing 210093
  • Received:2015-02-10 Revised:2015-03-02 Online:2015-07-25 Published:2015-03-19
  • Supported by:

    Project supported by the NSFC (No. 21002009), Major Program for the Natural Science Research of Jiangsu Colleges and Universities (Nos. 12KJA150002, 14KJA150002), Priority Academic Program Development of Jiangsu Higher Education Institution (PAPD), and Qing Lan Project of Jiangsu Province.

以氨基杯[4]芳烃为原料, 合成了五种手性杯[4]脯氨酸衍生物, 其结构经1H NMR, 13C NMR, IR, ESI-MS及元素分析表征. 运用核磁共振技术研究它们对扁桃酸对映异构体的手性识别性能, 结果表明5,11-二脯氨酰胺取代杯[4]芳烃2b对两种不同构型的扁桃酸异构体具有较好的选择性识别作用(KL/KD≈94). 提出可能的识别机理为分子间多种超分子相互协同作用, 包括酸碱作用、氢键和π···π堆积作用.

关键词: 杯[4]芳烃, L-脯氨酸, 扁桃酸, 手性识别, 核磁共振

Five chiral calix[4]proline derivatives were designed and synthesized from aminocalix[4]arenes, and their structures were characterized by 1H NMR, 13C NMR, IR, ESI-MS and elemental analysis. The chiral recognition ability for enantiomers of mandelic acid was investigated by NMR techniques, and the results showed that 5,11-diprolinamides substituted calix[4]arene 2b could well and selectively recognize the two enantiomers of mandelic acid (KL/KD≈94). A possible recognition mechanism was proposed, which was constructed by cooperative multi-supramolecular interactions including intermolecular acid-base, hydrogen bond and π···π stacking interactions.

Key words: calix[4]arene, L-proline, mandelic acid, chiral recognition, NMR