Base-mediated carboxylation of C-nucleophiles with CO2

Carbon dioxide (CO2) 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 CO2 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 C-nucleophiles is an environmentally friendly strategy for CO2 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 C-nucleophiles with CO2, based on the effects of nucleophiles, promoters, additives, and solvents. The types of pronucleophile are categorized as follows: hydrocarbon with C(sp3)–H, C(sp2)–H or C(sp)–H bonds, organosilanes, organotin, organoboron, and N-tosylhydrazones. Typical mechanisms and applications of these carboxylation reactions are also depicted. Moreover, mechanistic comprehension of CO2 activation and conversion at a molecular level aims to further expand the repertoire of carboxylation transformations mediated by bases.