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

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 beta-O-4 and beta-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, Sn-119 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 beta-O-4 and beta-1 lignin models were modest due to the formation of polymeric material stemming from direct ring hydroxylation.