Luo Yanlong, Huang Wenbin
School of Chemical Engineering and Technology, Tianshui Normal University, Tianshui, Gansu 741001, China.
Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China.
Org Biomol Chem. 2023 Nov 8;21(43):8628-8641. doi: 10.1039/d3ob01367g.
Carbon dioxide (CO) is an available, abundant, and renewable C1 resource, which could be converted into value-added chemicals. Due to its inherent thermodynamic stability and kinetic inertness, it is difficult to realize its efficient utilization. Nevertheless, many elegant strategies for the utilization of CO have been developed using Lewis bases, frustrated Lewis pairs, hydroxyl-containing compounds, amino-group-containing compounds or transition metal catalysis. Among them, base-mediated carboxylation of -nucleophiles is an environmentally friendly strategy for CO conversion, which is operationally simple, using low-toxicity bases and economical available promoters, without the use of complex ligands or cocatalysts. This review summarizes related work on the base-mediated carboxylation of -nucleophiles with CO, based on the effects of nucleophiles, promoters, additives, and solvents. The types of pronucleophile are categorized as follows: hydrocarbon with C(sp)-H, C(sp)-H or C(sp)-H bonds, organosilanes, organotin, organoboron, and -tosylhydrazones. Typical mechanisms and applications of these carboxylation reactions are also depicted. Moreover, mechanistic comprehension of CO activation and conversion at a molecular level aims to further expand the repertoire of carboxylation transformations mediated by bases.
二氧化碳（CO₂）是一种可得、丰富且可再生的C1资源，可转化为增值化学品。由于其固有的热力学稳定性和动力学惰性，难以实现其高效利用。然而，人们已经开发出许多利用路易斯碱、受阻路易斯对、含羟基化合物、含氨基化合物或过渡金属催化来利用CO₂的巧妙策略。其中，碱介导的亲核试剂羧化反应是一种环境友好的CO₂转化策略，操作简单，使用低毒碱和经济易得的促进剂，无需使用复杂配体或助催化剂。本综述基于亲核试剂、促进剂、添加剂和溶剂的影响，总结了碱介导的亲核试剂与CO₂羧化反应的相关工作。亲核前体的类型分类如下：具有C(sp)–H、C(sp²)–H或C(sp³)–H键的烃、有机硅烷、有机锡、有机硼和对甲苯磺酰腙。还描述了这些羧化反应的典型机理和应用。此外，在分子水平上对CO₂活化和转化的机理理解旨在进一步扩展碱介导的羧化转化反应的范围。
