An efficient organocatalytic method for chemoselective aerobic oxidation of secondary benzylic alcohols within lignin model compounds has been identified. Extension to selective oxidation in natural lignins has also been demonstrated. The optimal catalyst system consists of 4-acetamido-TEMPO (5 mol %; TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) in combination with HNO3 and HCl (10 mol % each). Preliminary studies highlight the prospect of combining this method with a subsequent oxidation step to achieve C-C bond cleavage.

We demonstrate an experimental approach for upgrading lignin that has been isolated from corn stover via biomass fractionation using γ-valerolactone (GVL) as a solvent. This GVL-based approach can be used in parallel with lignin upgrading to produce soluble carbohydrates at high yields (≥70%) from biomass without the use of enzymes, ionic liquids, or concentrated acids. The lignin was isolated after an initial hydrolysis step in which corn stover was treated in a high-solids batch reactor at 393 K for 30 min in a solvent mixture consisting of 80 wt% GVL and 20 wt% water. Lignin was isolated by precipitation in water and characterized by 2D HSQC NMR, showing that the extracted lignin was similar to native lignin, which can be attributed to the low acid level and the low extraction temperatures that are achievable using GVL as a solvent. This lignin was upgraded using a two-stage hydrogenolysis process over a Ru/C catalyst. The isolated lignin was first dissolved to form a mixture of 10% lignin, 80% THF, 8.5% H 3 PO 4 and 1.5% H 2 O, and treated at 423 K under hydrogen. The THF was removed by evaporation and replaced with heptane, forming a biphasic mixture. This mixture was then treated at 523 K in the presence of Ru/C and H 2 . The resulting heptane phase contained soluble lignin-derived monomers corresponding to 38% of the carbon in the original lignin. By adding 5% methanol during the second catalytic step, we produced additional monomers containing methyl esters and increased carbon yields to 48%. This increase in yield can be attributed to stabilization of carboxylic acid intermediates by esterification. The yield reported here is comparable to yields obtained with native lignin and is much higher than yields obtained with lignin isolated by other processes. These results suggest that GVLbased biomass fractionation could facilitate the integrated conversion of all three biomass fractions. Broader contextLignocellulosic biomass represents an attractive source of renewable carbon and could be used as a feedstock to substitute fossil-based fuels and chemicals. In addition, lignocellulosic biomass comprises non-edible plants that can grow on marginal lands and thus compete minimally with food production. In the context of increasing environmental issues related to climate change and because of increasing petroleum costs due to diminishing fossil reserves, it is urgent to find sustainable carbon-based substitutes to petroleum. However, growing, harvesting and processing biomass is often costly. Because of the expense of the raw material, the yield for conversion of biomass to useful products must be maximized. Lignocellulosic biomass typically contains about 50-70% polysaccharides (cellulose and hemicellulose) and 15-30% lignin by weight. Lignin is an irregular polymer composed of phenolic subunits. Given the relative uniformity of the carbohydrate polymers compared to lignin and the well-established chemical and biological upgrading pathways developed for sugar production and processing, much research and develop...