In this tutorial review recent mechanistic studies on transition metal-catalyzed hydrogen transfer reactions are discussed. A common feature of these reactions is that they involve metal hydrides, which may be monohydrides or dihydrides. An important question is whether the substrate coordinates to the metal (inner-sphere hydrogen transfer) or if there is a direct concerted transfer of hydrogen from the metal to substrate (outer-sphere hydrogen transfer). Both experimental and theoretical studies are reviewed.

The valorisation of the plant biopolymer lignin is now recognised as essential to enabling the economic viability of the lignocellulosic biorefining industry. In this context, the “lignin-first” biorefining approach, in...

Current processes for the fractionation of lignocellulosic biomass focus on the production of high-quality cellulosic fibers for paper, board, and viscose production. The other fractions that constitute a major part of lignocellulose are treated as waste or used for energy production. The transformation of lignocellulose beyond paper pulp to a commodity (e.g., fine chemicals, polymer precursors, and fuels) is the only feasible alternative to current refining of fossil fuels as a carbon feedstock. Inspired by this challenge, scientists and engineers have developed a plethora of methods for the valorization of biomass. However, most studies have focused on using one single purified component from lignocellulose that is not currently generated by the existing biomass fractionation processes. A lot of effort has been made to develop efficient methods for lignin depolymerization. The step to take this fundamental research to industrial applications is still a major challenge. This review covers an alternative approach, in which the lignin valorization is performed in concert with the pulping process. This enables the fractionation of all components of the lignocellulosic biomass into valorizable streams. Lignocellulose fractions obtained this way (e.g., lignin oil and glucose) can be utilized in a number of existing procedures. The review covers historic, current, and future perspectives, with respect to catalytic lignocellulose fractionation processes.

A tandem organosolv pulping and Pd-catalysed transfer hydrogenolysis depolymerisation and deoxygenation has been developed. The tandem process generated 2-methoxy-4-(prop-1-enyl)phenol in 23% yield (92% theoretical monomer yield) starting from pine wood and 2,6-dimethoxy-4-(prop-1-enyl)phenol in 49% yield (92% theoretical monomer yield) starting from birch wood. Only endogenous hydrogen from wood was consumed, and the reaction was performed using green solvents.

A reductive lignocellulose fractionation in a flow-through system in which pulping and transfer hydrogenolysis steps were separated in time and space has been developed.