One-flow syntheses of diverse heterocyclic furan chemicals directly from fructose via tandem transformation platform
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Abstract
The sustainable green chemistry associated with lignocellulosic biomass is of current interest for producing various chemical feedstocks via multi-step transformation processes. Here we introduce a chemical platform system for the multicomponent cascade transformation of natural lignocellulosic biomass resources. We demonstrate the concept by developing an integrated continuous two-step microfluidic system as a tandem transformation platform for direct conversion of fructose to diverse furan chemicals with excellent yields up to 99% via decarbonylation, etherification, oxidation and hydrogenolysis of a 5-hydroxymethylfurfural (HMF) intermediate. A sequential two-step process is utilized to complete the dehydration of fructose in the surface acid catalyst at 150 °C for 6 min, which is followed by the four types of HMF conversion in a binary or ternary phase to produce furfuryl alcohol (94% yield), 5-ethoxymethylfurfural (99%), 2,5-diformylfuran (82%) and 2,5-dimethylfuran (90%) with magnetic-based heterogeneous catalysts at 70–150 °C for 6–60 min. This innovative tandem microfluidic platform enables precise control of the reaction temperature and time for each individual biomass conversion step in a one-flow manner with no separation and purification steps for intermediates and catalysts. An innovative microfluidic platform can directly convert fructose biomass into valuable feedstocks. Dong-Pyo Kim's team from Pohang University of Science and Technology in Korea have developed a direct transformation device that pushes liquid solutions of sugars derived from waste cellulose through two sets of narrow tubes known as capillary microreactors. The first microreactor is loaded with sulfonic acid catalysts that dehydrate fructose molecules into smaller ring complexes called hydroxymethylfurfurals with complete conversion and 99% selectivity. The second stage features a clever system of external magnets that position iron-oxide-supported catalysts inside the microreactor to further transform the hydroxymethylfurfural into versatile furan chemicals widely used as synthetic building blocks. The team attributes the remarkable efficiency of their synthetic process to the one-flow design that eliminates the need for separation and purification steps. We report a tandem transformation platform for one-flow syntheses of diverse heterocyclic furan chemicals.
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Research context
OpenAlex topics: Catalysis for Biomass Conversion · Catalysis and Hydrodesulfurization Studies · Mesoporous Materials and Catalysis
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (33)
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1. Kunkes, E. L., Simonetti, D. A., West, R. M., Serrano-Ruiz, J. C., Gartner, C. A. & Dumesic, J. A. Catalytic conversion of biomass to monofunctional hydrocarbons and targeted liquid-fuel classes. Science 322, 417–421 (2008).10.1126/science.1159210 ↗
2. Xie, H. B., Zhao, Z. K. & Wang, Q. Catalytic conversion of inulin and fructose into 5-hydroxymethylfurfural by lignosulfonic acid in ionic liquids. ChemSusChem 5, 901–905 (2012).10.1002/cssc.201100588 ↗
3. Van Putten, R. J., Van der Waal, J. C., Jong, E., Rasrendra, C. B., Heeres, H. J. & Vries, J. G. Hydroxymethylfurfural, a versatile platform chemical made from renewable resources. Chem. Rev. 113, 1499–1597 (2013).10.1021/cr300182k ↗
4. Roman-Leshkov, Y., Chheda, J. N. & Dumesic, J. A. Phase modifiers promote efficient production of hydroxymethylfurfural from fructose. Science 312, 1933–1937 (2006).10.1126/science.1126337 ↗
5. Huang, Y. B., Yang, Z., Chen, M.-Y., Dai, J.-J., Guo, Q.-X. & Fu, Y. Heterogeneous palladium catalysts for decarbonylation of biomass-derived molecules under mild conditions. ChemSusChem 6, 1348–1351 (2013).10.1002/cssc.201300190 ↗
6. Halliday, G. A., Young, R. J. & Grushin, V. V. One-pot, two-step, practical catalytic synthesis of 2,5-diformylfuran from fructose. Org. Lett. 5, 2003–2005 (2003).10.1021/ol034572a ↗
7. Roman-Leshkov, Y., Barrett, C. J., Liu, Z. Y. & Dumesic, J. A. Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates. Nature 447, 982–U985 (2007).10.1038/nature05923 ↗
8. Yang, Z. Z., Deng, J., Pan, T., Guo, Q. X. & Fu, Y. A one-pot approach for conversion of fructose to 2,5-diformylfuran by combination of Fe3O4-SBA-SO3H and K-OMS-2. Green Chem. 14, 2986–2989 (2012).10.1039/c2gc35947b ↗
9. Takagaki, A., Takahashi, M., Nishimura, S. & Ebitani, K. One-pot synthesis of 2,5-diformylfuran from carbohydrate derivatives by sulfonated resin and hydrotalcite-supported ruthenium catalysts. Acs Catal. 1, 1562–1565 (2011).10.1021/cs200456t ↗
10. Broadwater, S. J., Roth, S. L., Price, K. E., Kobaslija, M. & McQuade, D. T. One-pot multi-step synthesis: a challenge spawning innovation. Org. Biomol. Chem. 3, 2899–2906 (2005).10.1039/b506621m ↗
11. Toure, B. B. & Hall, D. G. Natural product synthesis using multicomponent reaction strategies. Chem. Rev. 109, 4439–4486 (2009).10.1021/cr800296p ↗
12. Maurya, R. A., Park, C. P., Lee, J. H. & Kim, D. P. Continuous in situ generation, separation, and reaction of diazomethane in a dual-channel microreactor. Angew. Chem. Int. Ed. 50, 5952–5955 (2011).10.1002/anie.201101977 ↗
13. Basavaraju, K. C., Sharma, S., Maurya, R. A. & Kim, D. P. Safe use of a toxic compound: heterogeneous OsO4 catalysis in a nanobrush polymer microreactor. Angew. Chem. Int. Ed. 52, 6735–6738 (2013).10.1002/anie.201301124 ↗
14. Sharma, S., Maurya, R. A., Min, K. I., Jeong, G. Y. & Kim, D. P. Odorless isocyanide chemistry: an integrated microfluidic system for a multistep reaction sequence. Angew. Chem. Int. Ed. 52, 7564–7568 (2013).10.1002/anie.201303213 ↗
15. Webb, D. & Jamison, T. F. Continuous flow multi-step organic synthesis. Chem. Sci. 1, 675–680 (2010).10.1039/c0sc00381f ↗
16. Whitesides, G. M. The origins and the future of microfluidics. Nature 442, 368–373 (2006).10.1038/nature05058 ↗
17. Thorsen, T., Maerkl, S. J. & Quake, S. R. Microfluidic large-scale integration. Science 298, 580–584 (2002).10.1126/science.1076996 ↗
18. Jahnisch, K., Hessel, V., Lowe, H. & Baerns, M. Chemistry in microstructured reactors. Angew. Chem. Int. Ed. 43, 406–446 (2004).10.1002/anie.200300577 ↗
19. Kim, H., Nagaki, A. & Yoshida, J. A flow-microreactor approach to protecting-group-free synthesis using organolithium compounds. Nat. Commun. 2, 264 (2011).10.1038/ncomms1264 ↗
20. Marre, S. & Jensen, K. F. Synthesis of micro and nanostructures in microfluidic systems. Chem. Soc. Rev. 39, 1183–1202 (2010).10.1039/b821324k ↗
21. Gill, C. S., Price, B. A. & Jones, C. W. Sulfonic acid-functionalized silica-coated magnetic nanoparticle catalysts. J. Catal. 251, 145–152 (2007).10.1016/j.jcat.2007.07.007 ↗
22. Bae, J. A., Song, K.-C., Jeon, J.-K., Ko, Y. S., Park, Y.-K. & Yim, J.-H. Effect of pore structure of amine-functionalized mesoporous silica-supported rhodium catalysts on 1-octene hydroformylation. Micropor. Mesopor. Mat. 123, 289–297 (2009).10.1016/j.micromeso.2009.04.015 ↗
23. Geilen, F. M. A., Stein, T. V., Engendahl, B., Winterle, S., Liauw, M. A., Klankermayer, J. & Leitner, W. Highly selective decarbonylation of 5-(hydroxymethyl)furfural in the presence of compressed carbon dioxide. Angew. Chem. Int. Ed. 50, 6831–6834 (2011).10.1002/anie.201007582 ↗
24. Liu, A. Q., Liu, B., Wang, Y. M., Ren, R. S. & Zhang, Z. H. Efficient one-pot synthesis of 5-ethoxymethylfurfural from fructose catalyzed by heteropolyacid supported on K-10 clay. Fuel 117, 68–73 (2014).10.1016/j.fuel.2013.09.072 ↗
25. Wang, H. L., Deng, T., Wang, Y., Cui, X., Qi, Y., Mu, X., Hou, X. & Zhu, Y. Graphene oxide as a facile acid catalyst for the one-pot conversion of carbohydrates into 5-ethoxymethylfurfural. Green Chem. 15, 2379–2383 (2013).10.1039/c3gc41109e ↗
26. Su, C. L., Acik, M., Takai, K., Lu, J., Hao, S.-J., Zheng, Y., Wu, P., Bao, Q., Enoki, T., Chabal, Y. J. & Loh, K.P. Probing the catalytic activity of porous graphene oxide and the origin of this behaviour. Nat. Commun. 3, 1298 (2012).10.1038/ncomms2315 ↗
27. Petersen, T. P., Polyzos, A., O'Brien, M., Ulven, T., Baxendale, I. R. & Ley, S. V. The oxygen-mediated synthesis of 1,3-butadiynes in continuous flow: using Teflon AF-2400 to effect gas/liquid contact. ChemSusChem 5, 274–277 (2012).10.1002/cssc.201100339 ↗
28. Polyzos, A., O'Brien, M., Petersen, T. P., Baxendale, I. R. & Ley, S. V. The continuous-flow synthesis of carboxylic acids using CO2 in a tube-in-tube gas permeable membrane reactor. Angew. Chem. Int. Ed. 50, 1190–1193 (2011).10.1002/anie.201006618 ↗
29. O'Brien, M., Taylor, N., Polyzos, A., Baxendale, I. R. & Ley, S. V. Hydrogenation in flow: Homogeneous and heterogeneous catalysis using Teflon AF-2400 to effect gas-liquid contact at elevated pressure. Chem. Sci. 2, 1250–1257 (2011).10.1039/c1sc00055a ↗
30. Amarasekara, A. S., Green, D. & McMillan, E. Efficient oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran using Mn(III)-salen catalysts. Catal. Commun. 9, 286–288 (2008).10.1016/j.catcom.2007.06.021 ↗
31. Wang, G. H., Hilgert, J., Richter, F. H., Wang, F., Bongard, H.-J., Spliethoff, B., Weidenthaler, C. & Schuth, F. Platinum-cobalt bimetallic nanoparticles in hollow carbon nanospheres for hydrogenolysis of 5-hydroxymethylfurfural. Nat. Mater. 13, 294–301 (2014).
32. Thananatthanachon, T. & Rauchfuss, T. B. Efficient production of the liquid fuel 2,5-dimethylfuran from fructose using formic acid as a reagent. Angew. Chem. Int. Ed. 49, 6616–6618 (2010).10.1002/anie.201002267 ↗
33. Binder, J. B. & Raines, R. T. Simple chemical transformation of lignocellulosic biomass into furans for fuels and chemicals. J. Am. Chem. Soc. 131, 1979–1985 (2009).10.1021/ja808537j ↗