Highly selective and efficient solvent-free transformation of bio-derived levulinic acid to γ-valerolactone by Ru(II) arene catalyst precursors

The selective and efficient solvent-free hydrogenation of bio-based levulinic acid (LA) to γ-valerolactone (GVL)<br>was achieved with new pyridylimine ruthenium(II) complexes as catalyst precursors. The hydrogenation reactions<br>were performed in the presence of formic acid as hydrogen source using a catalyst loading as low as 0.1 mol<br>% with potassium hydroxide or triethylamine (Et3N). 4-Hydroxyvaleric acid (HVA) was produced only when<br>KOH was used, whereas reactions involving Et3N were selective to GVL. At 150 °C,>96% LA conversions were<br>achieved with 100% GVL selectivity. Recyclability of catalyst precursors was demonstrated by running three<br>consecutive reactions where 100% conversion and selectivity was maintained. In-situ NMR studies show that<br>hydrogen gas is formed by the decomposition of formic acid to carbon dioxide and hydrogen. Ru-hydride species<br>have been detected, by 1H NMR, and are believed to be the catalytically active species, and a mechanism of the<br>reaction has been proposed.