New ruthenium(II) isocyanide catalysts for the transfer hydrogenation of ethyl levulinate to γ-valerolactone in C2-C6 alcohols

Abstract

Transfer hydrogenation (TH) processes are receiving great attention for biomass valorization and ruthenium(II) complexes are renowned TH catalysts both on laboratory and industrial scale. Only a few homogeneous catalytic precursors are available in the literature for the TH of ethyl levulinate (EL) to γ-valerolactone (GVL). Herein, starting from simple, commercially available isocyanides, two classes of air-stable ruthenium(II) complexes were synthesized and tested as catalytic precursors. First, an optimized preparation of Ru(II) p-cymene isocyanide complexes was developed. Then, the thermally induced p-cymene/DMSO substitution gave access to unprecedented ruthenium isocyanide-DMSO complexes. All the complexes were characterized and tested in TH of EL to GVL showing promising performances, adopting 2-propanol as hydrogen donor, a low catalyst (Ru) and co-catalyst (KOH) amount, working under microwave heating for 1 h at 150 °C. The most selective systems were also successfully tested with different biomass-derived alcohols, including 2-butanol. Finally, the recycling of the best catalyst was also investigated, thus improving the efficiency of the entire process.