Prof. Arjan W. Kleij’s group has developed a halide-free catalytic process that uses carbon dioxide to selectively produce different families of cyclic compounds. Published in ACS Catalysis, the study shows how combining an aluminium-based catalyst with different organic bases can steer the reaction towards distinct products, expanding the possibilities for carbon dioxide conversion.
Carbon dioxide is increasingly explored as a renewable carbon source for chemical synthesis. Among the most studied processes is the production of cyclic carbonates, compounds with applications as synthetic intermediates and offering potential building blocks for new (polymeric) materials. These reactions commonly rely on catalytic systems containing halides, which upon scale up cause corrosive conditions and produce undesired waste, thus limiting their sustainability.
The group of Prof. Kleij has developed an alternative, halide-free catalytic system that enables the selective formation of either five- or seven-membered cyclic structures simply depending on the base catalyst used in the reaction. Mechanistic analysis also revealed how one of these structures (seven-membered) acts as a precursor for the formation of the other heterocycle (five-membered), helping the team to better understand the involved reactivity modes.
“While standard carbonate chemistry mainly focuses on new catalyst development, our group has a long tradition in developing synthetic applications using a wider pool of heterocycles,” says Prof. Kleij. “In the current case, we demonstrate that catalysts can be tweaked by judiciously choosing the catalytic base partner offering divergent access to five-, and more interestingly, exciting and new types of seven-membered heterocycles”.
According to the authors, the study demonstrates how small changes in catalyst design can broaden the range of carbon dioxide-derived molecules accessible through sustainable catalytic processes.
Reference publication
Halide-Free Heterocyclic Divergence from Carbon Dioxide Enabled by a Binary Lewis Acid/Base Catalyst
Chang, C.; Amos, S. G. E.; Benet-Buchholz, J.; Kleij, A. W.
ACS Catal. 2026
DOI: 10.1021/acscatal.6c02207
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