Reactivity of a benzylic lignin-carbohydrate model compound during enzymatic dehydrogenative polymerisation of coniferyl alcohol

Lignin is thought to be covalently bound to carbohydrates like hemicellulose during biosynthesis to form a lignin-carbohydrate complex (LCC). However, successive polymerisation with monolignols after the formation of LCC has not yet been clarified. To investigate the reaction of LCC, its enzymatic dehydrogenative polymerisation was conducted using deuterium-labelled coniferyl alcohol and model compounds, i.e., a lignin model (β-O-4 dimer model) compound (LM) and an LCC model (benzyl ether type) compound (LCCM). The obtained polymers (DHPs) were methylated and subjected to thioacidolysis, and the degradation products were quantified by gas chromatography-mass spectrometry (GC-MS). The results showed that the amount of coniferyl alcohol connected to the LCCM via β-O-4 binding was almost the same as that bound to the LM. However, the amount of unreacted LCCM was larger than that of LM, suggesting that the LCCM is less likely to form condensed structures, i.e., 5-5, β-5, and 4-O-5 structures. This could be due to the steric hindrance of the carbohydrate at the benzylic position.