钯催化二氧化碳为羰基源的羧基化反应  

Recent advances in the Pd-catalyzed carboxylation reactions using carbon dioxide as carbonyl source

作　　者：熊文芳 戚朝荣 江焕峰 Wenfang Xiong;Chaorong Qi;Huanfeng Jiang(Key Laboratory of Functional Molecular Engineering of Guangdong Province,School of Chemistry and Chemical Engineering,South China University of Technology,Guangzhou 510640,China)

机构地区：[1]华南理工大学化学与化工学院,广东省功能分子工程重点实验室,广州510640

出　　处：《科学通报》2021年第7期757-772,共16页Chinese Science Bulletin

基　　金：国家重点研发计划(2016YFA0602900);中国博士后科学基金(2018M640774);中央高校基本科研业务费(D2191970)资助。

摘　　要：二氧化碳是地球上蕴藏最为丰富的C1资源,其资源化利用一直是有机化学研究前沿及热点领域之一.其中,过渡金属催化以二氧化碳为羰基源的羧基化反应可以有效构建很多具有重要应用价值的羧酸及其衍生物,是实现二氧化碳资源化利用的理想途径之一,日益受到科学家的关注.钯是有机合成中用途最广的重要过渡金属之一,钯催化剂具有高反应活性、高选择性等特点,在二氧化碳羧基化反应中发挥重要的作用.本文主要聚焦于钯催化二氧化碳参与的形成碳-碳键的羧基化反应,着重从反应机理出发,分别阐述了各类烯丙基、芳基和烯烃等试剂与二氧化碳羧基化反应研究进展,并对这些反应进行总结以及对未来的发展方向进行展望.Carbon dioxide is the most abundant C1 resource on the Earth, and its resource utilization has been one of the hot spots and the frontiers research of organic chemistry. Among them, the transition metal catalyzed carboxylation reactions with carbon dioxide as carbonyl source provided high atom-economical strategies for the construction of an array of carboxylic acids and their derivatives, which were regarded as one of the most effective approaches for the utilization of carbon dioxide. In recent years, various transition metals such as nickel, copper, palladium, gold, rhodium, cobalt and iron have been widely applied in the carboxylation of carbon dioxide. Based on our research interest in palladium-catalyzed coupling reactions, in this paper, we reviewed the recent research progress of the Pd-catalyzed carboxylation with carbon dioxide as carbonyl source. There are several types of the Pd-catalyzed carboxylation reactions, including:(1) The Pd-catalyzed carboxylation reactions of the carbon dioxide with allylic, butadiene, allenes compounds, respectively, which underwent the nucleophilic addition of σ-allyl palladium species to carbon dioxide;(2) the Pd-catalyzed carboxylation reactions of the carbon dioxide with aryl bromides, aryl triflates, respectively, in which the aryl palladium species were generated via the oxidation addition of aryl reagents with Pd(0), followed by the insertion of carbon dioxide;(3) the Pd-catalyzed carboxylation reactions of the carbon dioxide with unactivated aryl sp2 C-H bonds, which proceeded the concertedmetalation-deprotonation process to produce the palladacycle intermediate, followed by the insertion of two molecules of carbon dioxide into the hetero-palladium bond of palladacycle intermediate;(4) the Pd-catalyzed carboxylation reaction of ethylene and carbon dioxide via the oxidation cycloaddition process to generate five-membered palladalactones intermediate;(5) the Pd-catalyzed carboxylation reactions of carbon dioxide with organozinc reagents, which underwent the transmet

关 键 词：二氧化碳 C1资源 钯催化 羧基化反应 

分 类 号：O621.251[理学—有机化学] X701[理学—化学]