Fluoroalkylated BINAP ligands have been evaluated in the ruthenium-catalysed asymmetric hydrogenation of dimethyl itaconate in supercritical CO 2 as well as MeOH. Fluoroalkylated BINAP ligands have been evaluated in the ruthenium-catalysed asymmetric hydrogenation of dimethyl itaconate in both MeOH and supercritical CO 2 (scCO 2 ). The reaction proceeds slower and gives a lower enantioselectivity in the latter, which is probably due to the lower polarity of scCO 2 .