Recent advances in cycloaddition of CO₂ with epoxides: halogen-free catalysis and mechanistic insights

Abstract

The atom-economical cycloaddition of CO₂ with epoxides to synthesize cyclic carbonates is a promising route for valuable utilization of CO₂. Halogenide such as alkali metal halides and quaternary ammonium salt have been developed as the efficient catalysts. However, the spilled halogen causes equipment corrosion and affects the product purity. To address these concerns, the halogen-free cycloaddition of CO₂ with epoxides has always been desired. In this review, we systematically discussed the halogen-free catalysis for cycloaddition of CO₂ with epoxides from the mechanistic insights, aiming to promote the development of efficient halogen-free catalysts. Two types of catalysts, i.e., alternatives of halogen nucleophiles for epoxide activation, and bifunctional catalysts with Lewis acid-base sites for synergistic activation of CO₂ and epoxides are summarized and emphasized. Specially, metal oxides as the potential halogen-free catalysts are highlighted due to their flexible acid-base sites for synergistic activation of CO₂ and epoxides, facile preparation, and low cost.

Graphical abstract

Keywords

carbon dioxide / halogen-free catalysis / cyclic carbonate / mechanistic insight

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Competing interests

The authors declare that they have no competing interests.

Acknowledgements

Financial support from the National Key R&D Program of China (Grant No. 2022YFB4101900), and National Natural Science Foundation of China (Grant Nos. 22278305 and U21B2096).

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