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.
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This material is based on work supported by the National Science Foundation under Cooperative Agreement No. 1355438. Funding from the British Council under the Global Innovation Initiative for the GB3-Net project is also gratefully acknowledged. The single-crystal diffractometer was funded by the NSF (MRI CHE-0319176). Diffuse reflectance UV-Vis spectra were measured at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility.
Jennings, John Adam; Parkin, Sean R.; Munson, Eric; Delaney, Sean; Calahan, Julie L.; Isaacs, Mark; Hong, Kunlun; and Crocker, Mark, "Regioselective Baeyer–Villiger Oxidation of Lignin Model Compounds with Tin Beta Zeolite Catalyst and Hydrogen Peroxide" (2017). Chemistry Faculty Publications. 92.