Notes on the Asymmetric Hydrogenation of Methyl Acetoacetate in Neoteric Solvents

Abstract

Asymmetric hydrogenation of methyl acetoacetate to methyl (R)-3-hydroxybutyrate by [(R)- RuCl(binap)(p-cymen)]Cl has been studied in methanol-ionic liquid and methanol- dense CO₂ solvent systems. The ionic pairs triethylhexylammonium and 1-methylimidazolium with bis(trifluoromethane sulfonyl) imide and hexafluorophosphates were used. The role of ionic pairs on the kinetic parameters and (enantio)selectivity has been demonstrated. Although the CO₂ expanded methanol system suffered from a reduction in both reaction rate and product selectivity, this changed in the presence of water. The high selectivity of the optimized methanol-CO₂-water-halide system was designed as a consequence of observed additive effects.