CATALYTIC CARBOXYLATIVE CYCLIZATION OF TERMINAL ACETYLENIC ALCOHOLS WITH CO₂: MODERN APPROACHES TO GREEN SYNTHESIS
Keywords:
carbon dioxide, terminal acetylenic alcohols, propargylic alcohols, carboxylative cyclization, α-alkylidene cyclic carbonates, CO₂ fixation, green synthesis, heterogeneous catalysis.Abstract
The catalytic carboxylative cyclization of terminal acetylenic alcohols with carbon dioxide represents an atom-efficient approach to the synthesis of α-alkylidene cyclic carbonates. Among terminal alkynols, propargylic alcohols are particularly suitable substrates because the adjacent hydroxyl and C≡C groups enable CO₂ incorporation followed by intramolecular cyclization. This review summarizes the development of homogeneous metal catalysts, organocatalysts, ionic liquids, heterogeneous metal-containing materials, and continuous-flow approaches. Particular attention is paid to reaction temperature, CO₂ pressure, catalyst recyclability, solvent requirements, and substrate scope. Comparative analysis indicates a progressive transition from high-pressure and noble-metal systems toward atmospheric-pressure, solvent-free, recyclable, and process-intensified catalytic technologies. Current achievements and remaining challenges in the sustainable production of α-alkylidene cyclic carbonates are discussed.
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