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  

Electrocarboxylation of Benzylic Phosphates and Phosphinates with Carbon Dioxide

作　　者：刘晓菲 王贺[1] 陶力[1] 任伟民[1] 吕小兵[1] 张文珍[1] Xiaofei Liu;He Wang;Li Tao;Weimin Ren;Xiaobing Lu;Wenzhen Zhang(State Key Laboratory of Fine Chemicals,Frontiers Science Center for Smart Materials,Dalian University of Technology,Dalian 116024,Liaoning Province,China)

机构地区：[1]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

出　　处：《物理化学学报》2024年第9期73-76,共4页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(22278054,21920102006);中央高校基本科研业务费专项资金(DUT22LAB609)资助项目。

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CO_(2)^(·-)的可能性。Carbon dioxide(CO_(2))serves as a nontoxic,abundant,cheap,and renewable C1 feedstock in synthetic chemistry.The synthesis of high valueadded fine chemicals,such as organic carboxylic acids,using CO_(2),is always a focal point of research.Due to the thermodynamic stability and kinetic inertness of carbon dioxide,traditional carboxylation reactions utilizing CO_(2) 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 CO_(2),provides a milder and more efficient route for CO_(2) utilization.Among these approaches,electrocarboxylation of organic halides or pseudohalides containing C—X bonds with CO_(2) 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 CO_(2) 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

关 键 词：电化学羧化反应 非牺牲阳极反应 二氧化碳 磷酸苄酯 芳基乙酸 

分 类 号：O646[理学—物理化学]