Substrate dependent synergetic and antagonistic interaction of ammonium halide and polyoxometalate catalysts in the synthesis of cyclic carbonates from oleochemical epoxides and CO2

Organic halides and polyoxometalates (POMs) were studied as catalyst systems for the insertion of carbon dioxide into epoxides originating from plant oils as biogenic feedstock. In the formation of methyl oleate carbonate, synergistic rate acceleration and increased cis-selectivity were observed using ammonium halide and transition metal substituted silicotungstate POMs catalysts in a combined system. Mechanistic insight into the cooperative action was gained by kinetic measurements and analysis of the stereochemical outcome of the reaction. For poly-epoxidised oleochemicals as substrates, the simple ammonium halide catalyst gave better performance as side reactions were encountered with the POM-containing system.