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离子液体催化二氧化碳与亲核试剂的反应

Ionic Liquids Catalysis for Carbon Dioxide Conversion With Nucleophiles.

作者信息

Xia Shu-Mei, Chen Kai-Hong, Fu Hong-Chen, He Liang-Nian

机构信息

State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, China.

Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin, China.

出版信息

Front Chem. 2018 Oct 8;6:462. doi: 10.3389/fchem.2018.00462. eCollection 2018.

Abstract

Carbon dioxide, as a promising C synthon, has attracted great interest in organic synthesis. Due to the thermodynamic stability and kinetic inertness of CO, developing efficient strategies for CO activation and subsequent conversion is very crucial. In this context, Ionic liquids (ILs) show great potential for capturing and activating CO owing to their unique structures and properties, making them become ideal alternatives to volatile organic solvents and/or catalysts for CO transformation. This minireview aims at summarizing ILs-promoted reactions of CO with -nucleophiles (primary amines)/-nucleophiles (primary alcohols, water). Two catalytic systems i.e., metal/ILs binary systems such as Cu/ILs systems and Ag/ILs systems as well as single ILs systems including anion-functionalized ILs and bifunctionalized ILs have been developed for CO catalytic conversion, for instance, carboxylative cyclization of nucleophiles e.g., propargylic alcohols, amines, 2-aminobenzonitriles and -aminobenzenethiol, and formylation of amines or 2-aminothiophenols with hydrosilanes to afford various value-added chemicals e.g., cyclic carbamates, unsymmetrical organic carbonates, α-hydroxyl ketones, and benzimidazolones. In a word, IL could provide a powerful tool for efficient CO utilization.

摘要

二氧化碳作为一种很有前景的碳合成子,在有机合成中引起了极大的关注。由于CO₂的热力学稳定性和动力学惰性,开发高效的CO₂活化及后续转化策略至关重要。在此背景下,离子液体(ILs)因其独特的结构和性质,在捕获和活化CO₂方面显示出巨大潜力,使其成为挥发性有机溶剂和/或用于CO₂转化的催化剂的理想替代品。本综述旨在总结离子液体促进的CO₂与亲核试剂(伯胺)/亲核试剂(伯醇、水)的反应。已开发出两种催化体系,即金属/离子液体二元体系,如Cu/离子液体体系和Ag/离子液体体系,以及单一离子液体体系,包括阴离子功能化离子液体和双功能化离子液体,用于CO₂催化转化,例如亲核试剂如炔丙醇、胺、2-氨基苯甲腈和苯硫酚的羧基环化反应,以及胺或2-氨基苯硫酚与硅烷的甲酰化反应,以提供各种增值化学品,如环状氨基甲酸酯、不对称有机碳酸酯、α-羟基酮和苯并咪唑酮。总之,离子液体可以为高效利用CO₂提供一个强大的工具。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6492/6186839/d211f9433ccf/fchem-06-00462-g0001.jpg

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