Continuous Asymmetric Hydrogenation in Supercritical Carbon Dioxide using an Immobilised Homogeneous Catalyst

Abstract

AbstractContinuous flow supercritical carbon dioxide (scCO2) has previously been shown (P. Stephenson, P. Licence, S. K. Ross, M. Poliakoff, Green Chem. 2004, 6, 521) to be a viable medium for conducting continuous asymmetric hydrogenation when it is combined with an appropriate enantioselective catalyst. Here we examine the use of a composite catalyst immobilisation system modified with several different types of asymmetric bisphosphine ligands in continuous flow scCO2. In particular, proprietary ligands from Solvias AG were found to be the most successful, with Josiphos 001 improving the enantiomeric excess (ee) to>80 % in the asymmetric hydrogenation of dimethyl itaconate (DMIT); this ee is higher than that reported for the batch hydrogenation of DMIT using a homogeneous catalyst fully dissolved in scCO2 (S. Lange, A. Brinkmann, P. Trautner, K. Woelk, J. Bargon, W. Leitner, Chirality 2000, 12, 450).