Issue 6, 2017

The effect of ring size on the selective carboxylation of cycloalkene oxides


Carbon dioxide utilisation technology can contribute to the reduction of atmospheric CO2 levels both through its sequestration from flue gases and indirectly by relieving pressure on conventional feedstocks in chemical manufacturing. A promising approach is to employ CO2 to produce valuable cyclic carbonates (CCs) in reaction with suitable epoxides. This also has the advantage that carbon dioxide replaces toxic and hazardous reactants such as phosgene. In earlier work we have investigated the synthesis of epoxides from cycloalkenes using supported gold and gold–palladium nanoparticles as catalysts and oxygen from air as the oxidant under solvent free conditions. A strong dependence of epoxide selectivity on ring size was observed with C5 < C6 < C7 ≪ C8. In this study we extend this work to the investigation of cycloaddition of CO2 to different cycloalkene oxides with the ultimate aim of designing a process in which both epoxidation of an alkene and incorporation of CO2 could be achieved in a single process. However, we have found the opposite trend for the selectivity to carbonates: smaller ring cycloalkene oxides giving the highest carbonate selectivities while large rings do not yield CCs at all. The product distributions suggest that an alternative ring opening of the epoxides to yield alcohols and ketones is preferred under all the experimental conditions explored for larger ring systems. Additionally, the mechanism of the CC synthesis using a quaternary ammonium salt and ZnBr2 as the catalyst system was investigated using DFT methods. The results of the calculations support the experimental findings.

Graphical abstract: The effect of ring size on the selective carboxylation of cycloalkene oxides

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Article information

Article type
22 Nov 2016
06 Mar 2017
First published
07 Mar 2017
This article is Open Access
Creative Commons BY license

Catal. Sci. Technol., 2017,7, 1433-1439

The effect of ring size on the selective carboxylation of cycloalkene oxides

R. Alsaiari, L. T. Perrott, E. Nowicka, R. V. Engel, P. J. Miedziak, S. A. Kondrat, J. K. Edwards, D. J. Willock and G. J. Hutchings, Catal. Sci. Technol., 2017, 7, 1433 DOI: 10.1039/C6CY02448C

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