Intensification of the use of ionic liquids as efficient reaction co-solvents in asymmetric hydrogenations

The “Noyori” Ru-BINAP chiral complex is an industrially used homogeneous catalyst for stereoselective hydrogenations providing valuable fine chemicals with high optical yields. Its pseudo-immobilisation with help of various ionic liquids (ILs) represents an alternative to the not very efficient heterogenisation on inorganic supports. Many ILs are commercially readily available or could simply be produced, but in both cases a problem of their purity is encountered. Presence of even trace impurities may either suppress or promote the reaction progress, and most importantly, the parameter of enantioselectivity. The complex treatment of the reaction system must be always accepted whenever a genuine role of an ionic liquid is discussed. For this purpose a well understood reaction system—asymmetric hydrogenation of methyl-3-oxobutanoate (methylacetoacetate/MAA) to methyl-3-hydroxybutanoate (methylhydroxybutyrate/MHB) over the chiral Noyori type Ru-BINAP catalyst in the ethanol–bmimPF6 reversibly biphasic mixed phase was chosen. Self-prepared bmimPF6 ionic liquid was exposed to a series of normalized purification steps based on a theoretical semi-mechanistic model. It provided a clear evidence of the number and duration of necessary purification steps together with an effective “value” of each of them. Another important data were collected in the form of pseudo-ternary phase diagrams for all major components including the model impurities.