Regioselective Baeyer–Villiger oxidation of lignin model compounds with tin beta zeolite catalyst and hydrogen peroxide

Abstract

Lignin depolymerization represents a promising approach to the sustainable production of aromatic molecules. One potential approach to the stepwise depolymerization of lignin involves oxidation of the benzylic alcohol group in β-O-4 and β-1 linkages, followed by Baeyer–Villiger oxidation (BVO) of the resulting ketones and subsequent ester hydrolysis. Towards this goal, BVO reactions were performed on 2-adamantanone, a series of acetophenone derivatives, and lignin model compounds using a tin beta zeolite/hydrogen peroxide biphasic system. XRD, ¹¹⁹Sn MAS NMR spectroscopy, DRUVS and XPS were used to determine tin speciation in the catalyst, the presence of both framework Sn and extra framework SnO₂ being inferred. Conversion of ketones to BVO products was affected by electron donation as well as steric hindrance, 4′-methoxyacetophenone affording the highest yield of ester (81%). As the size and complexity of the ketone increased, excess hydrogen peroxide was typically needed for successful BVO. Yields of ester products derived from β-O-4 and β-1 lignin models were modest due to the formation of polymeric material stemming from direct ring hydroxylation.