Carbonylation with CO2

Carbon dioxide (CO2) is an ideal C1 source in organic synthesis since it is non-toxic, abundant, easily accessible and recyclable. Despite a lot of challenges such as thermodynamic stability and kinetic inertness, many research groups have already made significant progress in the application of CO2 to synthesize valuable carbonyl-containing compounds, which are commonly produced by phosgene or oxidative carbonylation with carbon monoxide (CO). The toxicity of carbonylation reagents is a main drawback and many of these methods are limited by the demand of (sub)stoichiometric metal oxidants. As the carbon in CO2 shows the highest valence state, higher than that in CO, CO2 might play a similar role to the combination of CO and oxidants, which can be considered as “CO2 = CO + [O]”. In this chapter, we mainly discuss the process by which CO2 is used as a carbonyl source of carbonylation of different chemical bonds.