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

引用本文: 江黎黎, 郑少瑜, 刘雪娇, 谢小敏. 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[J]. 大学化学, 2025, 40(7): 267-276. doi: 10.12461/PKU.DXHX202408004 shu

Citation: Lili Jiang, Shaoyu Zheng, Xuejiao Liu, Xiaomin Xie. Copper-Catalyzed Oxidative Coupling Reactions for the Synthesis of Aryl Sulfones: A Fundamental and Exploratory Experiment for Undergraduate Teaching[J]. University Chemistry, 2025, 40(7): 267-276. doi: 10.12461/PKU.DXHX202408004 shu

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.
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

通讯作者: 谢小敏，Email: xiaominxie@sjtu.edu.cn

基金项目:
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)

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:

English

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

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

Corresponding author: Xiaomin Xie, xiaominxie@sjtu.edu.cn

Received Date: 10 August 2024
Revised Date: 04 November 2024
Available Online: 15 January 2025

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

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

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

通讯作者: 谢小敏，Email: xiaominxie@sjtu.edu.cn

English

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

Corresponding author: Xiaomin Xie, xiaominxie@sjtu.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

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

通讯作者: 谢小敏，Email: xiaominxie@sjtu.edu.cn

English

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

Corresponding author: Xiaomin Xie, xiaominxie@sjtu.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

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