Design of novel nitrogenous base-tethered Co-Schiff base complexes for the selective catalytic cleavage of lignin Rebecca E. Key and Joseph J. Bozell Center.

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Presentation transcript:

Design of novel nitrogenous base-tethered Co-Schiff base complexes for the selective catalytic cleavage of lignin Rebecca E. Key and Joseph J. Bozell Center for Renewable Carbon The University of Tennessee November 10, 2016

Lignin Second most abundant renewable carbon source after cellulose Example of native poplar lignin Second most abundant renewable carbon source after cellulose Comprises up to 25% of biomass Biorefining processes for isolating lignin introduce drastic changes into the native structure Increase in the number of free phenolic groups Vanholme, R.; Demedts, B.; Morreel, K.; Ralph, J.; Boerjan, W. Plant Physiol. 2010, 153, 895. Bozell, J. J. Top Curr Chem 2014, 353, 229. Robert, D. R.; Bardet, M.; Gellerstedt, G.; Lindfors, E. L. J. Wood Chem. Technol. 1984, 4, 239.

Catalysis of phenolic reactions Substituted aromatics in lignin are electron-rich Susceptible to phenolic oxidation Catalysts that target lignin-like phenol oxidation would be a viable approach for determining applicability of lignin as a chemical feedstock Co-Schiff bases catalyze phenolic oxidation under aerobic conditions. Biannic, B.; Bozell, J. J.; Elder, T. Green Chem. 2014, 16, 3635. Zombeck, A.; Drago, R. S.; Corden, B. B.; Gaul, J. H. J. Am. Chem. Soc. 1981, 103, 7580. Co-salen-pyridine complex designed by Peter Ciesielski, NREL

Co-Schiff base catalysis: previous work Bozell, J. J.; Hanes, B. R.; Dimmel, D. R. J. Org. Chem. 1995, 60, 2398.

Mechanism for Co-Schiff-base-catalyzed phenolic oxidation Bozell, J. J.; Hanes, B. R.; Dimmel, D. R. J. Org. Chem. 1995, 60, 2398. Nishinaga, A.; Tomita, H. J. Mol. Catal. 1980, 7, 179. Zombeck, A.; Drago, R. S.; Corden, B. B.; Baul, J. H. J. Am. Chem. Soc. 1981, 103, 7580. Corden, B. B.; Drago, R. S.; Perito, R. P. J. Am. Chem. Soc. 1985, 107, 2903.

Co-Schiff base catalysis: previous work Bozell, J. J.; Hanes, B. R.; Dimmel, D. R. J. Org. Chem. 1995, 60, 2398.

Co-Schiff base catalysis: addition of a hindered base Conjugate Acid pKa Yield MMBQ (%) None N/A 21 DABCO 8.19 DIPEA 10.98 55 DIPA 10.76 51 TEA 10.60 52 DBU 13.28 Cedeno, D.; Bozell, J. J. Tetrahedron Lett. 2012, 53, 2380.

Mechanism for Co-Schiff-base-catalyzed phenolic oxidation using a hindered base Cedeno, D.; Bozell, J. J. Tetrahedron Lett. 2012, 53, 2380.

Second-generation Co-Schiff base catalysts Loading (mol %) Reaction Time (h) Yield 2,6-DMBQ (%) Yield SyCHO SyOH Recovery 1, NBn 5 1 74 19 2, NH 61 25 trace 3, NMe 16 54 40 4, NPh 2 65 22 5, Pip 75 Biannic, B.; Bozell, J. J. Org. Lett. 2013, 15, 2730.

Alternative nitrogenous Cobalt-Schiff base catalysts: Expanding the scope of bulky, nitrogeneous base substituents

Arylpiperazine-tethered Co-Schiff base catalysts: expanding the scope Previously Synthesized Catalysts New Catalysts

Symmetric Asymmetric Holbach, M.; Zheng, Z.; Burd, C.; Jones, C. W.; Weck, M. J. Org. Chem. 2006, 71, 2903. Biannic, B.; Bozell, J. J. Org. Lett. 2013, 15, 2730.

Catalyst. Time (h) 2,6-DMBQ (%) SyCHO (%) SyOH (%) 1*, asymm-NBn 1 74 19 1, asymm-NBn 18 71 4 - 4*, asymm-NPh 2 65 22 5*, asymm-Piperidine 16 75 6, symm-Bn 21.5 76 11 7-asymm-diPhMe 9 8, asymm-Phenethyl 10, symm-diPhMe 67 *Biannic, B.; Bozell, J. J. Org. Lett. 2013, 15, 2730.

Catalyst Time (h) MMBQ (%) 2,5-DMBQ (%) Vanillin (%) VaOH (%) 1*, asymm-NBn 16 83 NR 7-asymm-diPhMe 18 34 5 - 21 8, asymm-Phenethyl 17 (DCM) 38 33 *Biannic, B.; Bozell, J. J. Org. Lett. 2013, 15, 2730.

Summary: Ar-piperazine-tethered-Co-salen-catalyzed S and G unit oxidations S Models Catalysts 7-9: Comparable yield of 2,6-DMBQ relative to lead catalyst 1 Catalyst 10: Activity TBD G Models Catalysts 7-8: Low yield of MMBQ relative to lead catalyst 1 Catalyst 6, 9-10: Activity TBD Are increases in side chain bulk altering the steric environment between the catalytically active species and substrate? Computational analyses: TBD

Catalyst Time (h) 2,6-DMBQ (%) SyCHO (%) SyOH (%) 20, asymm-Pyrrolidine 18.5 19 49 - 21, asymm-Dimethylamine 47 20 1, asymm-NBn 18 71 4 22, symm-Pyrrolidine 24 26 21 23, symm-Dimethylamine 48 11

Copper-Schiff Base Catalysis

Laccase Cu-containing oxidase Deconstructs lignin and lignin models Tadesse, M. A.; D’Aggibale, A. D.; Galli, C.; Gentili, P.; Sergi, F. Org. Biomol. Chem. 2008, 6, 868. Morozova, O. V.; Shumakovich, G. P.; Schleev, S. V.; Yaropolov, Y. I. Appl. Biochem. Microbiol. 2007, 43, 523.

Cu Catalysts: Benzyl Alcohol Oxidation BnOH Aldehyde Yield (%) 88 90 Jiang, J.-A.; Du, J.-L.; Wang, Z.-G.; Zhang, Z.-N.; Xu, X.; Zheng, G.-L.; Yi, Y-F. Tetrahedron Lett. 2014, 55, 1677.

Water-Soluble Metallo-Schiff Bases Haikarainen, A.; Sipila, J.; Pietikainen, P.; Pajunen, A.; Mutikainen, I. Bioorg. Med. Chem. 2001, 9, 1633.

Cu-Schiff Base Catalysts Kannan, M; Punniyamurthy, T.; Tetrahedron: Asymmetry 2014, 125, 1331.

Catalyst Solvent Time (h) MMBQ (%) 2,5-DMBQ (%) Vanillin (%) VaOH (%) Cu-Salen 25 MeOH: H2O (1:1) 23 - 88 MeOH: DCM (1:1) 90 64 iPrOH 42 >99 DCM 18 3 20

Water-soluble Cu-Schiff base WO2008/132474 A1 Haikarainen, A.; Sipilc, J.; Pietikainen, P.; Pajunen, A.; Mutikainen, I. J. Chem. Soc. Dalton Trans., 2001, 991. Minutolo, F.; Pini, D>; Petri, A.; Salvadori, P. Tetrahedron: Asymmetry, 1996, 7, 2293.

Overall summary of studies Activity regarding phenolic oxidation of lignin models is being examined Synthesis and characterization of homogeneous (symmetric and asymmetric) metallo-Schiff base catalysts are ongoing Active catalysts will be tested for ability to deconstruct lignin Expand the library of nitrogeneous base-tethered Co-Schiff base and novel metallo-Schiff base catalysts for phenolic oxidation New methodology for the conversion of biorefinery lignin Streamline biorefinery operation Offer new catalytic routes to biobased chemicals and fuels from renewable carbon sources

Acknowledgements Professor Joseph Bozell Bozell Group UT Biological and Small Molecule Mass Spectrometry Core (BSMMC) Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio) Director: Professor Maureen McCann, Purdue University DOE, Basic Energy Sciences DE-SC0000997

Biannic, B.; Bozell, J. J.; Elder, T. Green Chem. 2014, 16, 3635.