Stabilization of reactive intermediates is an enabling concept in biomass fractionation and depolymerization. Deep eutectic solvents (DES) are intriguing green reaction media for biomass processing; however undesired lignin condensation is a typical drawback for most acid-based DES fractionation processes. Here we describe ternary DES systems composed of choline chloride and oxalic acid, additionally incorporating ethylene glycol (or other diols) that provide the desired ‘stabilization’ function for efficient lignocellulose fractionation, preserving the quality of all lignocellulose constituents. The obtained ethylene-glycol protected lignin displays high β-O-4 content (up to 53 per 100 aromatic units) and can be readily depolymerized to distinct monophenolic products. The cellulose residues, free from condensed lignin particles, deliver up to 95.9 ± 2.12% glucose yield upon enzymatic digestion. The DES can be recovered with high yield and purity and re-used with good efficiency. Notably, we have shown that the reactivity of the β-O-4 linkage in model compounds can be steered towards either cleavage or stabilization, depending on DES composition, demonstrating the advantage of the modular DES composition.
The transition from a petroleum-based infrastructure to an industry which utilises renewable resources is one of the key research challenges of the coming years. Biomass, consisting of inedible plant material that does not compete with our food production, is a suitable renewable feedstock. In recent years, much research has been focused on developing new chemical strategies for the valorisation of different biomass components. In addition to the many heterogeneous and enzymatic approaches, homogenous catalysis has emerged as an important tool for the highly selective transformation of biomass, or biomass derived platform chemicals. This Perspective provides an overview of the most important recent developments in homogeneous catalysis towards the production and transformation of biomass and biomass related model compounds. The chemical valorisation of the main components of lignocellulosic biomass – lignin and (hemi)cellulose is reviewed. In addition, important new catalyst systems for the conversion of triglycerides and fatty acids are presented.