大学化学 >> 2025, Vol. 40 >> Issue (7): 267-276.doi: 10.12461/PKU.DXHX202408004

所属专题： 有机化学课程与实验教学(2024)

化学实验 上一篇    下一篇

铜催化氧化偶联反应合成芳基砜类化合物——适合本科生的基础探究教学实验

江黎黎1, 郑少瑜2, 刘雪娇2, 谢小敏2   

  1. 1 上海交通大学分析测试中心, 上海 200240;
    2 上海交通大学化学化工学院, 上海 200240
  • 收稿日期:2024-08-10 录用日期:2024-11-04 发布日期:2025-07-01
  • 通讯作者: 谢小敏 E-mail:xiaominxie@sjtu.edu.cn
  • 基金资助:
    上海交通大学教学设计创新专项(CTLD24D0004)；上海交通大学化学化工学院教学改革研究项目(CHTR2202)

Copper-Catalyzed Oxidative Coupling Reactions for the Synthesis of Aryl Sulfones: A Fundamental and Exploratory Experiment for Undergraduate Teaching

Lili Jiang1, Shaoyu Zheng2, Xuejiao Liu2, Xiaomin Xie2   

  1. 1 Instrumental Analysis Center, Shanghai Jiao Tong University, Shanghai 200240, China;
    2 School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
  • Received:2024-08-10 Accepted:2024-11-04 Published:2025-07-01
  • Contact: Xiaomin Xie E-mail:xiaominxie@sjtu.edu.cn

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摘要： 过渡金属催化偶联反应是非常重要的现代有机合成方法，但由于一些反应条件及催化剂的价格限制，尚未在本科实验教学中大规模推广。为了让学生切身体会现代有机化学的发展及绿色化学理念，我们设计了一个反应条件温和、操作步骤简单、原料及催化剂廉价易得的过渡金属催化偶联反应——铜催化芳基硼酸与烷基亚磺酸盐的氧化偶联反应合成芳基砜类化合物。以醋酸铜和N-甲基咪唑为催化剂、空气作为氧化剂，催化4-乙酰基苯硼酸及甲基亚磺酸钠的偶联反应，以中等产率得到4-甲砜基苯乙酮。本实验包括无水实验操作、微量试剂的称量及加料、薄层色谱及旋转蒸发技术、熔点测定等实验操作。此外，本实验可以拓展为探究实验，让学生初步学习有机合成实验研究方法及数据处理、分析方法，了解过渡金属催化有机反应中主要的影响因素，培养学生科学研究的思维，提高学生的综合化学素养。本实验已经在本科生实验教学中进行了验证。

关键词: 过渡金属催化偶联反应, 铜催化氧化偶联反应, 芳基砜类化合物, 基础实验教学, 探究实验教学

Abstract: Transition-metal-catalyzed coupling reactions are among the most important methodologies in modern organic synthesis. However, due to the cost of catalysts and specific reaction conditions, these reactions have not been widely adopted in undergraduate laboratory courses. To allow students to experience the development of modern organic chemistry and the principles of green chemistry firsthand, we designed a copper-catalyzed oxidative coupling reaction between aryl boronic acids and alkyl sulfinates to synthesize aryl sulfones. The reaction uses copper acetate (Cu(OAc)₂) and N-methylimidazole as catalysts, with air as the oxidant. The coupling of 4-acetylphenylboronic acid with sodium methylsulfonate results in the formation of 4-(methylsulfonyl)phenyl ethanone in moderate yield. This experiment involves anhydrous techniques, microscale reagent handling, thin-layer chromatography, rotary evaporation, and melting point determination. Additionally, the experiment can be extended into an exploratory exercise, enabling students to investigate the key factors influencing transition metal-catalyzed organic reactions. It fosters the development of scientific research skills and enhances students' overall experimental competence. The experiment has been successfully implemented in undergraduate laboratory courses.

Key words: Transition metal catalyzed coupling reaction, Copper catalyzed oxidative coupling reaction, Aryl sulfones, Fundamental experiment teaching, Exploratory experiment teaching