Beyond Conventional Catalysis: Recent Paradigm Shifts in CO ₂ –Epoxide Cycloaddition

As atmospheric carbon dioxide (CO 2 ) concentrations continue to rise due to anthropogenic activities, it necessitates the capture, storage, and transformation of CO 2 into greener and more versatile resources. Among the various strategies, the cycloaddition of CO 2 with epoxides to form cyclic carbonates is a noteworthy route owing to its 100% atom economy and the wide industrial applications. However, due to high kinetic inertness and thermodynamic stability of CO 2 , an efficient catalytic system that operates under milder conditions is desirable. This review focuses on recent advances in both homogeneous and heterogeneous catalysis, focusing upon the catalytic mechanisms and efficiency of the known catalytic systems, e.g., amines, frustrated Lewis pairs (FLPs), N‐heterocyclic carbenes (NHCs), ionic liquids (ILs), metal–organic frameworks (MOFs), and graphitic carbon nitrides (g‐C 3 N 4 ). Furthermore, we highlight both the current challenges and the future directions aimed at developing sustainable and efficient CO 2 –epoxide conversions, with an outlook on the development of novel catalytic systems for scalable production of cyclic carbonates.