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Cyclic Carbonate Synthesis: History
Please note this is an old version of this entry, which may differ significantly from the current revision.
Subjects: Chemistry, Organic
Contributor: Helena Kang

Five-membered cyclic carbonates arise principally from cycloaddition of carbon dioxide to an epoxide, a transformation that inserts CO2 as the carbonyl and one ring oxygen of the heterocycle. Mechanistically, a Lewis acid activates the epoxide toward ring opening by a nucleophilic cocatalyst (halide or related anion); the resulting alkoxide captures CO2, and the carbonate anion displaces the leaving group to close the five-membered ring [1]. Bimetallic aluminium–salen complexes catalyze this sequence with two metal centers cooperating in epoxide activation and nucleophilic delivery [2]. One-component catalysts incorporate both the Lewis-acidic and the nucleophilic functions in a single molecular species, so that no external cocatalyst is required [3]. Alternative routes include oxidative carbonylation of diols and rearrangement of acyclic carbonates, but the epoxide–CO2 coupling is the defining contemporary construction. The product is a cyclic organic carbonate, distinct from polycarbonates (which may form if the intermediate alkoxide polymerizes) and from acyclic dialkyl carbonates.

  • cyclic carbonate
  • epoxide–CO2 coupling
  • carbon dioxide fixation
  • Lewis acid–base catalysis

Organic Chemistry Synthesis Methods • Organic Chemistry • Chemistry • Physical Sciences

References

  1. Michael North; Riccardo Pasquale; Mechanism of Cyclic Carbonate Synthesis from Epoxides and CO2. Angew. Chem. Int. Ed. 2009, 48, 2946-2948, 10.1002/anie.200805451.
  2. William Clegg; Ross W. Harrington; Michael North; Riccardo Pasquale; Cyclic Carbonate Synthesis Catalysed by Bimetallic Aluminium–Salen Complexes. Chem. – A Eur. J. 2010, 16, 6828-6843, 10.1002/chem.201000030.
  3. Jaisiel Meléndez; Michael North; Pedro Villuendas; One-component catalysts for cyclic carbonate synthesis. Chem. Commun. 2009, 2009, 2577-2579, 10.1039/b900180h.
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