Base-mediated carboxylation of C-nucleophiles with CO2

Abstract

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.