Halide-free pyridinium base binary organocatalyst for the cycloaddition of carbon dioxide to epoxides

The cycloaddition of carbon dioxide to epoxide (CCE) reaction stands out as one of the few feasible chemical processes for catalytically fixing CO₂. Traditionally, halide anions were frequently used as cocatalysts for catalysing the CCE reaction owing to their excellent nucleophilic and leaving abilities. However, halides are known for their corrosive effects on process reactors, and their treatment is challenging. Consequently, there is a substantial increase in the demand for halide-free catalysis in the CCE reaction. Herein, a series of bifunctional catalysts were designed for CCE reactions. The reactions were assessed under conditions of 120 °C and 1 MPa employing a catalyst loading of 0.5 mol% over 24 hours. The dual activation mechanism of the catalyst was confirmed through NMR titration and control experiments. As a bifunctional catalyst, the ion pair polarized the oxygen atom of epoxide via H-bonding with N⁺-H while the phenolate anion activated carbon dioxide simultaneously. This study introduces a pyridinium base binary organocatalyst as a halide-free hydrogen bond donor (HBD) anion organocatalyst with broad applicability for CO₂ utilization.