Combined lignin defunctionalisation and synthesis gas formation by acceptorless dehydrogenative decarbonylation

Abstract

The valorization of lignin, consisting of various phenylpropanoids building blocks, is hampered by its highly functionalized nature. The absence of the γ-carbinol group in an unnatural C2 β-O-4 motif compared to the native lignin C3 β-O-4 motif provides great opportunities for developing new valorization routes. Thus efficient defunctionalisation approaches that transform the C3 β-O-4 motif into a simplified C2 β-O-4 motif are of interest. Based on a study with a series of model compounds, we established a feasible application of an iridium-catalysed acceptorless dehydrogenative decarbonylation method to efficiently remove the γ-carbinol group in a single step. This defunctionalisation generates valuable synthesis gas, which can be collected as a reaction product. By this direct catalytic transformation, a yield of ∼70% could be achieved for a C3 β-O-4 model compound that was protected from undergoing retro-aldol cleavage by alkoxylation of the benzylic secondary alcohol in the α position. A phenylcoumaran model compound containing a γ-carbinol group as well as a benzylic primary alcohol also proved to be reactive under dehydrogenative decarbonylation conditions, which can further contribute to the reduction of the structural complexity of lignin. Notably, the liberation of synthesis gas was confirmed and the signals for the defunctionalized C2 β-O-4 motif were observed when this dehydrogenative decarbonylation approach was applied on organosolv lignins. This selective defunctionalized lignin in conjunction with the formation of synthesis gas has the potential to enhance the development of profitable and sustainable biorefineries.