Osmium catalyzed asymmetric dihydroxylation of methyl trans-cinnamate in ionic liquids, followed by supercritical CO2 product recovery

In this work, osmium-catalyzed asymmetric dihydroxylation (AD) of methyl trans-cinnamate was studied. Osmium and chiral ligand catalysts were immobilized in ionic liquid only, without any other reaction solvents, while the recovery of the product was performed by extraction with supercritical CO2, and compared with results obtained by extractions with organic solvents such as hexane and diethyl ether. In supercritical CO2 extraction experiments, optimal extraction pressure was found and ionic liquid chosen, so that the highest reaction yields coupled with lowest osmium content in the crude product can be achieved. Finally, recycle experiments of the same (ionic liquid + catalytic system) mixture were successfully conducted. Application of ionic liquids and supercritical CO2 in osmium catalyzed AD allows for the isolation of the diol basically without contamination with osmium, in high yield and enantiomeric excess, and it makes possible the efficient reuse of ionic liquid solvent and the catalytic system.

Graphical abstractThe combination of ionic liquids as a solvent in the asymmetric Sharpless dihydroxylation (AD) of methyl trans-cinnamate and the use of scCO2 in the separation process allows a very simple, efficient, clean and robust system for the reuse of the AD catalytic system.Figure optionsDownload full-size imageDownload as PowerPoint slide