磷酸苄酯和亚磷酸苄酯衍生物与二氧化碳的电化学羧化反应

引用本文: 刘晓菲, 王贺, 陶力, 任伟民, 吕小兵, 张文珍. 磷酸苄酯和亚磷酸苄酯衍生物与二氧化碳的电化学羧化反应[J]. 物理化学学报, 2024, 40(9): 230700. doi: 10.3866/PKU.WHXB202307008 shu

Citation: Xiaofei Liu, He Wang, Li Tao, Weimin Ren, Xiaobing Lu, Wenzhen Zhang. Electrocarboxylation of Benzylic Phosphates and Phosphinates with Carbon Dioxide[J]. Acta Physico-Chimica Sinica, 2024, 40(9): 230700. doi: 10.3866/PKU.WHXB202307008 shu

磷酸苄酯和亚磷酸苄酯衍生物与二氧化碳的电化学羧化反应

大连理工大学精细化工国家重点实验室, 智能材料化工前沿科学中心, 辽宁大连 116024

通讯作者: 张文珍, zhangwz@dlut.edu.cn

基金项目:
国家自然科学基金 22278054

国家自然科学基金 21920102006

中央高校基本科研业务费专项资金 DUT22LAB609

摘要: 二氧化碳是无毒、储量丰富、廉价易得的可再生能源，以二氧化碳作为碳源，将其催化转化为高附加值的化学品比如羧酸化合物，对实现碳循环可持续利用具有重要的意义。由于二氧化碳的热力学稳定性和动力学惰性，传统的二氧化碳参与的羧化反应通常需要苛刻的反应条件。与经典的有机合成方法相比，有机电化学合成利用电能驱动反应，不需要额外的化学氧化剂或还原剂，是更安全、可持续和环保经济的有机合成方法。其中，碳卤键或碳杂键与二氧化碳的电化学还原羧化反应可高效获得高附加值羧酸化合物。磷酸酯作为一种良好的离去基团广泛应用于众多有机合成反应。本文发展了在牺牲阳极及非牺牲阳极两种体系中磷酸苄酯和亚磷酸苄酯衍生物与二氧化碳的电化学羧化反应高效合成重要的芳基乙酸类化合物。该反应表现出优异的官能团耐受性，高效且容易放大，为布洛芬、非诺洛芬等芳基乙酸类药物分子提供了一种高效经济绿色的合成方法。通过循环伏安实验和多组对照实验证实磷酸苄酯和亚磷酸苄酯底物在阴极还原生成的苄基自由基和碳负离子是反应关键中间体，同时也不能排除二氧化碳在阴极还原生成CO₂^•−的可能性。

关键词:

English

Electrocarboxylation of Benzylic Phosphates and Phosphinates with Carbon Dioxide

State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, Dalian University of Technology, Dalian 116024, Liaoning Province, China

Corresponding author: Wenzhen Zhang, Email: zhangwz@dlut.edu.cn; Tel.: +86-411-84986257

Received Date: 03 July 2023
Accepted Date: 27 July 2023
Revised Date: 27 July 2023
Available Online: 15 September 2024
Fund Project:
the National Natural Science Foundation of China

the National Natural Science Foundation of China

the Fundamental Research Funds for the Central Universities, China

Abstract: Carbon dioxide (CO₂) serves as a non-toxic, abundant, cheap, and renewable C1 feedstock in synthetic chemistry. The synthesis of high value-added fine chemicals, such as organic carboxylic acids, using CO₂, is always a focal point of research. Due to the thermodynamic stability and kinetic inertness of carbon dioxide, traditional carboxylation reactions utilizing CO₂ often require harsh reaction conditions. However, organic electrochemical synthesis, which employs electrons as clean reagents to drive the reaction and avoids additional chemical oxidants or reductants, has emerged as a safer, more economical, highly selective, sustainable, and environmentally friendly method for preparing fine chemicals. Electrocarboxylation, which leverages organic electrochemical synthesis to catalytically transform CO₂, provides a milder and more efficient route for CO₂ utilization. Among these approaches, electrocarboxylation of organic halides or pseudohalides containing C―X bonds with CO₂ has been extensively investigated as a means to access value-added carboxylic acids. Phosphates, known for their good leaving group properties, find extensive applications in organic synthesis. Under reductive conditions, the radical anion generated by benzyl phosphate easily dissociates into a benzyl radical and a phosphate anion. Hence, it can serve as an attractive substrate for participating in electrocarboxylation reactions. In this study, we report the highly efficient electrocarboxylation of benzylic phosphate and phosphinate derivatives using CO₂ as the carboxyl source. The constant current reaction took place in an undivided cell, employing glassy carbon as the cathode, and magnesium as the sacrificial anode, in a mixed solvent of DMF and THF. Additionally, this mild electrolysis can be carried out under nonsacrificial anode conditions, using cheap carbon felt electrode as both the nonsacrificial anode and cathode and N, N-diisopropylethylamine as an external reductant, therefore provided operationally simple and highly efficient synthetic method toward aryl acetic acids in moderate to good yield. The broad substrate scope, simple operation, facile scalability, and highly efficient transformation of phosphates into high value-added aryl acetic acids under mild conditions demonstrate the potential applicability of this reaction. To gain insight into the possible reaction mechanism, several control experiments were conducted. Isotope-labeling ¹³CO₂ experiment, cyclic voltammetry experiments, radical trapping reactions, and deuterium-labeling experiment indicated that cathodically generated benzylic radical and benzylic anion were key intermediates. Moreover, the single electron reduction of CO₂ to CO₂^•− might also occur during the reaction.

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沈阳化工大学材料科学与工程学院沈阳 110142

磷酸苄酯和亚磷酸苄酯衍生物与二氧化碳的电化学羧化反应

通讯作者: 张文珍, zhangwz@dlut.edu.cn

English

Electrocarboxylation of Benzylic Phosphates and Phosphinates with Carbon Dioxide

Corresponding author: Wenzhen Zhang, Email: zhangwz@dlut.edu.cn; Tel.: +86-411-84986257

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

中国化学会秘书处

磷酸苄酯和亚磷酸苄酯衍生物与二氧化碳的电化学羧化反应

通讯作者: 张文珍, zhangwz@dlut.edu.cn

English

Electrocarboxylation of Benzylic Phosphates and Phosphinates with Carbon Dioxide

Corresponding author: Wenzhen Zhang, Email: zhangwz@dlut.edu.cn; Tel.: +86-411-84986257

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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