Phosphorus‐based Bifunctional Organocatalysts for the Addition of Carbon Dioxide and Epoxides

Bifunctional phosphonium salts were synthesized and employed as organocatalysts for the atom efficient synthesis of cyclic carbonates from CO 2 and epoxides for the first time. These catalysts were obtained in high yields by a modular, straightforward one‐step synthesis. The hydrogen‐bond donating alcohol function in the side chain leads to a synergistic effect accelerating the catalytic reaction. The desired cyclic carbonates are obtained in high yields and selectivity under solvent‐free reaction conditions without the use of any co‐catalyst. Under optimized reaction conditions various epoxides were converted to the corresponding cyclic carbonates in excellent yields. The products were obtained analytically pure after simple filtration over a silica gel pad. This protocol is even applicable for a multigram reaction scale. Moreover, the catalysts could be easily recovered and reused up to five times.