大学化学 >> 2024, Vol. 39 >> Issue (5): 1-10.doi: 10.3866/PKU.DXHX202309053

所属专题： 第4届全国大学生化学实验创新设计大赛

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基于激发态手性铜催化的烯烃E→Z异构的动力学拆分——推荐一个本科生综合化学实验

李岩1, 王鑫泽1, 姚雪1, 俞寿云1,2   

  1. 1 南京大学化学化工学院, 南京 210023;
    2 化学国家级实验教学示范中心(南京大学), 南京 210023
  • 收稿日期:2023-09-14 修回日期:2024-01-05 发布日期:2024-01-31
  • 通讯作者: 俞寿云 E-mail:yushouyun@nju.edu.cn
  • 基金资助:
    基础学科拔尖学生培养计划2.0研究课题

Kinetic Resolution Enabled by Photoexcited Chiral Copper Complex-Mediated Alkene E→Z Isomerization: A Comprehensive Chemistry Experiment for Undergraduate Students

Yan Li1, Xinze Wang1, Xue Yao1, Shouyun Yu1,2   

  1. 1 School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China;
    2 National Demonstration Center for Experimental Chemistry Education, Nanjing University, Nanjing 210023, China
  • Received:2023-09-14 Revised:2024-01-05 Published:2024-01-31
  • Contact: Shouyun Yu E-mail:yushouyun@nju.edu.cn

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摘要： 外消旋体的拆分是制备光学活性化合物的重要方法，利用拆分试剂通过结晶进行的物理拆分，往往只能得到一种高光学活性的化合物。作为重要的不对称合成技术，动力学拆分可以获得高光学活性的产物，同时回收高光学活性的原料。我们综合光催化和动力学拆分技术，设计了一例基于激发态手性铜催化的烯烃E→Z异构的动力学拆分实验，实验包括底物的制备和纯化、光催化反应、动力学拆分曲线的绘制以及对照实验等内容，包含无水无氧操作、柱层析和pTLC分离、GC和手性HPLC分析等多项实验操作，涵盖了化学合成、表征、动力学测量等。本实验综合性高，操作性强，总时长24学时，分为三天完成，也可开设为三个8学时的独立实验，适合在有机化学实验或综合化学实验课程中开设。通过本实验可以锻炼学生的综合实验技能，让学生了解学科前沿，感受到动力学拆分、光催化和激发态过渡金属催化技术的优越性和重要性，并激发学生进一步推动该领域的发展。

关键词: 动力学拆分, 光激发态铜, 过渡金属催化, 烯烃E→Z异构

Abstract: Resolution is one of the most important methods for the preparation of optically active compounds. Classic physical resolution via crystallization assisted by chiral resolution reagents can usually provide one compound with highly optical purity. As an important asymmetric synthetic technology, kinetic resolution has become a powerful tool for the construction of multifunctional enantioenriched molecules and has been widely used in the synthesis of drugs and natural products. Therefore, we designed a kinetic resolution experiment based on alkene E→Z isomerization catalyzed by a photoexcited chiral copper complex. This experiment involves substrate synthesis, separation and purification, photocatalytic reaction, kinetic resolution curve drawing and condition verification. Many experimental skills are concerned in this experiment, including column chromatography separation, (preparative) thin layer chromatography (TLC), gas chromatography (GC) and chiral high-performance liquid chromatography (HPLC), which can not only exercise students’ comprehensive experimental skills, but also let students feel the advantages of kinetic resolution, photocatalysis and excited transition metal catalysis technologies. The experiment is designed reasonably with strong operability and high safety. It lasts 24 hours in total, including three one-day individual experiments. It is very suitable for the courses of organic chemistry experiment or comprehensive chemistry experiment.

Key words: Kinetic resolution, Photoexcited copper, Transition metal catalysis, Alkene E→Z isomerization