Carboxylate-Assisted Carboxylation of Thiophene with CO2 in the Solvent-Free Carbonate Medium

Direct carboxylation of thiophene with CO2 has been achieved under a relatively mild solvent-free carbonate and carboxylate medium. This base-mediated medium can cleave the very weakly acidic C–H bond without using other limiting reagents, which is one indispensable step in the carboxylation reaction. Product yield varies with different carboxylate salts, and cesium pivalate is the most suitable base additive among targeted simple carboxylate salts. Furthermore, the detailed mechanism of this carboxylation reaction is studied, which involves initial proton abstraction, rendered by carbonate and C–C bond formation, by inserting CO2. The activation energy barrier of the C–H activation step is higher than the following CO2 insertion step, whether for the formation of the mono- and/or di-carboxylate, which indicates that the C–H deprotonation induced by the base is slow and the resulting carbon-centered nucleophile reacts rapidly with CO2.