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综述与进展

过渡金属催化不饱和烃与有机金属试剂及CO2的串联羧化反应研究进展

易雅平a, 杭炜a, 席婵娟a,b   

  1. a 清华大学化学系生命有机磷化学及化学生物学教育部重点实验室 北京 100084;
    b 南开大学元素有机化学国家重点实验室 天津 300071
  • 收稿日期:2020-07-04 修回日期:2020-08-14 出版日期:2030-01-01 发布日期:2020-09-09
  • 通讯作者: 席婵娟 E-mail:cjxi@tsinghua.edu.cn
  • 基金资助:
    国家自然科学基金(Nos.21871163,91645120,and 21472106)资助项目.

Recent Advance of Transition-Metal-Catalyzed Tandem Carboxylation Reaction of Unsaturated Hydrocarbons with Organometallic Reagents and CO2

Yi Yapinga, Hang Weia, Xi Chanjuana,b   

  1. a MOE Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology, Department of Chemistry, Tsinghua University, Beijing 100084, China;
    b State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China
  • Received:2020-07-04 Revised:2020-08-14 Online:2030-01-01 Published:2020-09-09
  • Supported by:
    Project supported by the the National Natural Science Foundation of China (Nos. 21871163, 91645120, and 21472106)

二氧化碳(CO2)作为一碳合成子具有储量丰富、无毒无污染、绿色清洁等优点,因此在有机化学领域使用CO2作为一碳合成子反应一直以来受到广泛的关注。过渡金属催化不饱和烃与CO2反应合成羧酸是CO2作为一碳合成子的重要应用之一,这类反应可以通过串联羧化的策略实现,过渡金属催化不饱和烃先与有机金属试剂反应在原位生成新的有机金属试剂,之后再与CO2完成羧化。常用的有机金属试剂如格氏试剂、有机锌试剂和有机铝试剂均能够完成这类反应。本文根据不饱和烃的类别,并根据羧化反应的类型进一步分为不饱和烃的氢羧化反应和碳羧化反应,介绍过渡金属催化不饱和烃与有机金属试剂及CO2的串联羧化反应。

关键词: 二氧化碳, 不饱和烃, 羧化反应, 过渡金属催化, 有机金属试剂

Carbon dioxide (CO2), as a one-carbon synthon, has many advantages such as abundant, non-toxic, clean and so on. So the reactions using CO2 as a one-carbon synthon have been widely concerned in organic chemistry. Transition-metal-catalyzed reaction of unsaturated hydrocarbons with CO2 to produce carboxylic acid is one of the most commonly-used method to convert CO2, and organometallic reagents can be added to the reaction as reducing agent. This kind of reaction can be realized by the strategy of tandem reaction. In the reaction, the unsaturated hydrocarbons react with transition-metal catalysts and organometallic reagents to generate new organometallic reagents in situ first, and then complete carboxylation with CO2. Common organometallic reagents such as organozinc reagents, Grignard reagents, and organoaluminum reagents can all achieve this kind of carboxylation reaction. In this review, reactions are divided according to the type of unsaturated hydrocarbons, and each type can also be divided into hydrocarboxylation and carbocarboxylation. This review would introduce reaction according to this classification.

Key words: Carbon Dioxide, Unsaturated Hydrocarbons, Carboxylation Reaction, Transition-Metal Catalysts, Organometallic