摘要
作为可再生的碳一资源,二氧化碳的化学转化具有重要的生态意义和经济价值.苯炔是高活性的中间体,其参与的二氧化碳的化学转化反应可以实现苯环邻位同时构建两个官能团的策略,在温和条件下有效构筑C_(芳基)-C_(CO2)键,得到精细化学品中重要的中间体芳香羧酸类化合物.本文总结了苯炔经由亲核试剂驱动参与的二氧化碳的多组分反应,以及过渡金属催化的反应,并着重描述其反应特性和反应机理.
The concentration of CO2 in atmosphere has increased rapidly since the Industrial Revolution(by the time of May 2019, it has reached 414.7 ppm). Being one of the main greenhouse gases, CO2 has been widely blamed to be responsible for global warming. From the view point of chemistry, CO2 is also regarded as a sustainable and alternative carbon resource due to its nontoxic, low-cost and abundant. The use of CO2 as a C1 raw material instead of toxic phosgene or CO in organic synthesis has important ecological significance and economic value. However, only few industrial-scale chemical processes have been developed that use CO2 as a carbon source. The main reason for this is the chemical inertness associated with its thermodynamic and kinetic stability. In order to overcome such barriers, numerous useful synthetic methodologies by using highly active catalysts and reactant with a relatively high free energy have been developed for the incorporation of CO2 to organic compounds, such as carbonates, oxazolidinones, quinazolidine-2,4-diones.Arynes, which have been widely used in various carbon-carbon and carbon-heteroatom bond synthesis, have highly strained C≡C bonds and low lying lowest unoccupied molecular orbitals(LUMOs). Therefore, various nucleophiles such as amines, isocyanides, and imines can add to arynes, and the resultant zwitterions can be trapped by an electrophilic third component, thus leading to various three-component coupling reactions of high significance. When CO_(2) is used as the third component, thus constitutes a convenient method to install CO_(2) moiety directly to the aromatic ring, offering an excellent alternative access to aromatic carboxylic compounds. For example, Yoshida and co-workers reported the incorporation of CO_(2) in arynes multicomponent coupling triggered by imines and amines for the straightforward synthesis of benzoxazinones and anthranilic acid, respectively. Biju and co-workers disclosed the synthesis of phthalimides by a nulticomponent reaction involving arynes, isocyanid
作者
刘岚
马然
Lan Liu;Ran Ma(Shaanxi Key Laboratory of Chemical Additives for Industry,College of Chemistry and Chemical Engineering,Shaanxi University of Science&Technology,Xi'an 710021,China)
出处
《科学通报》
EI
CAS
CSCD
北大核心
2021年第7期739-747,共9页
Chinese Science Bulletin
基金
陕西省自然科学基础研究计划(2019JQ-037)
中国博士后科学基金(2019M650253)资助。
关键词
苯炔
亲核试剂
二氧化碳转化
多组分反应
芳香羧酸衍生物
arynes
nucleophiles
CO_(2)transformation
multicomponent reaction
aromatic carboxylic compounds
