Organocatalyzed Synthesis of Oleochemical Carbonates from CO sub(2) and Renewables

Bifunctional phosphorus-based organocatalysts proved to be highly efficient for the atom-economic reaction of CO sub(2) and epoxidized oleochemicals. Notably, those products are obtained from CO sub(2) and renewable feedstocks only. Structure-activity relationships have been deduced from a screening of 22 organocatalysts in a test reaction. Bifunctional catalysts based on a phosphonium salt bearing a simple phenolic moiety proved to be extraordinarily active under comparatively mild and solvent-free reaction conditions. In the presence of the most active organocatalyst 12 oleochemical carbonates were isolated in excellent yields up to 99%. This organocatalyzed reaction represents an excellent example for the realization of the 12 Principles of Green Chemistry as well as the 12 Principles of CO sub(2) Chemistry. Putting CO sub(2) to good use: Products based on >99% CO sub(2) are obtained by combining biological and chemical CO sub(2) fixation. Bifunctional phosphorus-based organocatalysts are highly active for the production of oleochemical cyclic carbonates under mild and solvent-free conditions, and structure-activity relationships can be deduced. This reaction represents an excellent example for green and sustainable chemistry.