New catalytic protocol expands synthetic potential of carbon dioxide

A newly developed protocol from the group of Prof. Arjan W. Kleij significantly expands the chemical space of larger-ring carbonates (and related carbamates) in fine chemical/polymer research programs. This advancement addresses a long-standing challenge in the synthesis of cyclic carbonates, particularly those with seven- or eight-membered rings, which have been difficult to produce efficiently by any means.

The research presents a catalytic approach for converting carbon dioxide (CO₂) into these heterocycles initially using a two-step process but later on also via a one-pot approach. This method relies on a silver-catalysed alkyne/CO₂ coupling followed by a base-catalysed ring expansion, overcoming limitations that previously restricted the synthesis to smaller five- and six-membered rings. Importantly, this catalytic strategy avoids the formation of more stable, undesired by-products and demonstrates good functional group tolerance.

The study, published in Nature Communications, highlights the growing interest in utilizing CO₂ as a sustainable and versatile carbon feedstock. The newly synthesised larger-ring cyclic carbonates and carbamates have shown unique potential as intermediates for pharma- and fine-chemical focused synthons. The protocol facilitates, for instance, the preparation of bicyclic oxazolidinone pharmacores through an intramolecular domino sequence as well as intermolecular transformations.

“This cascade process with properly designed substrates incorporating built-in pro-nucleophilic sites holds great future promise for the creation of complex synthons derived from carbon dioxide as feedstock,” says Prof. Arjan W. Kleij.

By expanding the portfolio of larger-ring heterocycles derived from CO₂, this work opens new incentives for fine-chemical, pharma-focused and polymer development further establishing its value in modern synthetic and catalytic chemistry.

Reference publication
Catalytic transformation of carbon dioxide into seven-membered heterocycles and their domino transformation into bicyclic oxazolidinones
Shi, W.; Benet-Buchholz, J.; Kleij, A. W.
Nat. Commun. 2025, 16, 1372
DOI: 10.1038/s41467-025-56681-5