Cholinium Pyridinolate Ionic Pair-Catalyzed Fixation of CO into Cyclic Carbonates.

A halide-free ionic pair organocatalyst was proposed for the cycloaddition of CO into epoxide reactions. Cholinium pyridinolate ionic pairs with three different substitution positions were designed. Under conditions of temperature of 120 °C, pressure of 1 MPa CO, and catalyst loading of 5 mol %, the optimal catalyst cholinium 4-pyridinolate ([Ch][4-OP]) was employed. After a reaction time of 12 h, styrene oxide was successfully converted into the corresponding cyclic carbonate, and its selectivity was improved to 90%. A series of terminal epoxides were converted into cyclic carbonates within 12 h, with yields ranging from 80 to 99%. The proposed mechanism was verified by H NMR and C NMR titrations. Cholinium cations act as a hydrogen bond donor to activate epoxides, and pyridinolate anions combine with carbon dioxide to form intermediate carbonate anions that attack epoxides as nucleophiles and lead to ring opening. In summary, a halide-free ionic pair organocatalyst was designed and the catalytic mechanism in the cycloaddition of CO into epoxides reactions was proposed.