有机小分子催化的炔丙醇与二氧化碳羧化环化反应  

The carboxylative cyclization of propargyl alcohol and carbon dioxide catalyzed by organocatalysts

作　　者：周瑞年 闫绍瑞 张帅 Ruinian Zhou;Shaorui Yan;Shuai Zhang(College of Chemistry and Material Science,Shandong Agricultural University,Tai'an 271018,China)

机构地区：[1]山东农业大学化学与材料科学学院,泰安271018

出　　处：《科学通报》2021年第7期748-756,共9页Chinese Science Bulletin

基　　金：国家博士后基金(2019M652447);山东省自然科学基金博士基金(ZR2017BB025);山东省高等学校青创人才引育计划资助。

摘　　要：对有机小分子催化二氧化碳(CO_(2))与炔丙醇羧化环化合成环状碳酸酯的反应体系进行概述,重点介绍离子液体、CO_(2)加合物和有机膦在催化炔丙醇羧化环化反应中的研究进展.有机小分子化合物能够与CO_(2)生成CO_(2)加合物或者亲核进攻炔丙醇中碳碳三键生成两性离子中间体,从而活化CO_(2)和(或)炔丙醇底物,催化此羧化环化反应.本文对有机小分子催化此羧化环化反应的机理进行了简要分析和探讨,希望为进一步发展更加高效、绿色的有机小分子催化体系提供一点思路.Carbon dioxide(CO2), as a cheap, non-toxic, and abundant C1 resource, can be transformed into high value-added chemicals by constructing C-C, C-O, C-N, and C-S bonds, which is in agreement with the requirements of green chemistry and sustainable development. For example, CO_(2) can not only be transformed into fuel-related formic acid,methanol etc., but also serves as raw materials for the synthesis of fine chemicals such as carbonates, carbamates and salicylic acid. However, CO_(2) has the disadvantage of thermodynamic stability and chemical inertness, which can hinder its chemical conversion and utilization. It has become one of the research hotspots to develop efficient catalysts of activating CO_(2) and reducing the reaction energy barrier in the field of CO_(2) conversion. Under the continuing efforts of chemists, a series of highly efficient catalysts have been developed and applied in the catalytic conversion of CO2. The carboxylative cyclization of propargyl alcohol to prepare α-alkylidene cyclic carbonates is one of desired chemical reaction in CO_(2) fixation, which presents 100% atomic utilization and meets the requirements of green chemistry.Now, investigations on the carboxylative cyclization of propargyl alcohol and CO_(2) have been developing rapidly, and a series of novel reaction systems have been reported. In the carboxylative cyclization, transition metals are extensively studied. Various transition-metal catalytic systems, including silver(AgⅠ), copper(CuⅠ), zinc(ZnⅡ), are closely investigated in the carboxylative cyclization. The transition-metal salts can effectively activate the carbon-carbon triple bond in the propargyl alcohol structure, facilitating the subsequent attack of carbon-carbon triple bonds by alkyl carbonate anions to generate the target products. Although the transition metals are efficient catalysts in this cyclization reaction, their disadvantages, such as high cost and transition-metal residues, are not favourable.Recently, transition metal-free organocatalysts have

关 键 词：二氧化碳 有机小分子催化剂 炔丙醇 羧化环化 

分 类 号：TQ225.52[化学工程—有机化工] TQ426[环境科学与工程—环境工程] X701