Organocatalytic Upgrading of Furfural and 5-Hydroxymethyl Furfural to C10 and C12 Furoins with Quantitative Yield and Atom-Efficiency

Zang, Hongjun; Chen, Eugene

doi:10.3390/ijms16047143

Organocatalytic Upgrading of Furfural and 5-Hydroxymethyl Furfural to C₁₀ and C₁₂ Furoins with Quantitative Yield and Atom-Efficiency

Journal Article · Mon Mar 30 00:00:00 EDT 2015 · International Journal of Molecular Sciences (Online)

DOI:https://doi.org/10.3390/ijms16047143· OSTI ID:1628374

Zang, Hongjun ^[1]; Chen, Eugene ^[2]

Colorado State Univ., Fort Collins, CO (United States). Dept. of Chemistry; DOE/OSTI
Colorado State Univ., Fort Collins, CO (United States). Dept. of Chemistry

There is increasing interest in the upgrading of C₅ furfural (FF) and C₆ 5-hydroxymethyl furfural (HMF) into C₁₀ and C₁₂ furoins as higher energy-density intermediates for renewable chemicals, materials, and biofuels. This work utilizes the organocatalytic approach, using the in situ generated N,S-heterocyclic carbene catalyst derived from thiazolium ionic liquids (ILs), to achieve highly efficient self-coupling reactions of FF and HMF. Specifically, variations of the thiazolium IL structure have led to the most active and efficient catalyst system of the current series, which is derived from a new thiazolium IL carrying the electron-donating acetate group at the 5-ring position. For FF coupling by this IL (0.1 mol %, 60 °C, 1 h), when combined with Et₃N, furoin was obtained in >99% yield. A 97% yield of the C₁₂ furoin was also achieved from the HMF coupling by this catalyst system (10 mol % loading, 120 °C, 3 h). On the other hand, the thiazolium IL bearing the electron-withdrawing group at the 5-ring position is the least active and efficient catalyst. The mechanistic aspects of the coupling reaction by the thiazolium catalyst system have also been examined and a mechanism has been proposed.

View Accepted Manuscript (DOE)

Research Organization:: Colorado State Univ., Fort Collins, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0005413

OSTI ID:: 1628374

Journal Information:: International Journal of Molecular Sciences (Online), Journal Name: International Journal of Molecular Sciences (Online) Journal Issue: 4 Vol. 16; ISSN 1422-0067

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

References (58)

An Efficient Nucleophilic Carbene Catalyst for the Asymmetric Benzoin Condensation Enders, Dieter; Kallfass, Ulrike Angewandte Chemie International Edition, Vol. 41, Issue 10 https://doi.org/10.1002/1521-3773(20020517)41:10<1743::aid-anie1743>3.0.co;2-q	journal	May 2002
Production of High-Quality Diesel from Biomass Waste Products Corma, Avelino; de la Torre, Olalla; Renz, Michael Angewandte Chemie, Vol. 123, Issue 10 https://doi.org/10.1002/ange.201007508	journal	January 2011
Preparation, Structure, and Reactivity of 1,3,4-Triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene, a New Stable Carbene Enders, Dieter; Breuer, Klaus; Raabe, Gerhard Angewandte Chemie International Edition in English, Vol. 34, Issue 9 https://doi.org/10.1002/anie.199510211	journal	May 1995
Synergies between Bio- and Oil Refineries for the Production of Fuels from Biomass Huber, George W.; Corma, Avelino Angewandte Chemie International Edition, Vol. 46, Issue 38, p. 7184-7201 https://doi.org/10.1002/anie.200604504	journal	September 2007
Metal-Free Dehydration of Glucose to 5-(Hydroxymethyl)furfural in Ionic Liquids with Boric Acid as a Promoter Ståhlberg, Tim; Rodriguez-Rodriguez, Sergio; Fristrup, Peter Chemistry - A European Journal, Vol. 17, Issue 5 https://doi.org/10.1002/chem.201002171	journal	January 2011
Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering Huber, George W.; Iborra, Sara; Corma, Avelino ChemInform, Vol. 37, Issue 52 https://doi.org/10.1002/chin.200652240	journal	December 2006
Chemical Routes for the Transformation of Biomass into Chemicals Corma, Avelino; Iborra, Sara; Velty, Alexandra ChemInform, Vol. 38, Issue 36 https://doi.org/10.1002/chin.200736263	journal	September 2007
ChemInform Abstract: Technology Development for the Production of Biobased Products from Biorefinery Carbohydrates - The US Department of Energy′s “Top 10” Revisited Bozell, Joseph J.; Petersen, Gene R. ChemInform, Vol. 41, Issue 28 https://doi.org/10.1002/chin.201028264	journal	June 2010
Synthesis of 5-(Hydroxymethyl)furfural in Ionic Liquids: Paving the Way to Renewable Chemicals Ståhlberg, Tim; Fu, Wenjing; Woodley, John M. ChemSusChem, Vol. 4, Issue 4 https://doi.org/10.1002/cssc.201000374	journal	January 2011
Furfural-A Promising Platform for Lignocellulosic Biofuels Lange, Jean-Paul; van der Heide, Evert; van Buijtenen, Jeroen ChemSusChem, Vol. 5, Issue 1 https://doi.org/10.1002/cssc.201100648	journal	December 2011
Diesel and Alkane Fuels From Biomass by Organocatalysis and Metal-Acid Tandem Catalysis Liu, Dajiang; Chen, Eugene Y. -X. ChemSusChem, Vol. 6, Issue 12 https://doi.org/10.1002/cssc.201300476	journal	August 2013
Benzoin condensation reactions of 5-membered heterocyclic compounds Lee, Chang Kiu; Kim, Mi Soon; Gong, Jin Soon Journal of Heterocyclic Chemistry, Vol. 29, Issue 1 https://doi.org/10.1002/jhet.5570290127	journal	January 1992
Asymmetric Organocatalysis Houk, K. N.; List, Benjamin Accounts of Chemical Research, Vol. 37, Issue 8 https://doi.org/10.1021/ar040216w	journal	August 2004
Applications of Ionic Liquids in Carbohydrate Chemistry: A Window of Opportunities El Seoud, Omar A.; Koschella, Andreas; Fidale, Ludmila C. Biomacromolecules, Vol. 8, Issue 9 https://doi.org/10.1021/bm070062i	journal	September 2007
Organocatalysis by N-Heterocyclic Carbenes Enders, Dieter; Niemeier, Oliver; Henseler, Alexander Chemical Reviews, Vol. 107, Issue 12, p. 5606-5655 https://doi.org/10.1021/cr068372z	journal	December 2007
Thiamin Diphosphate Catalysis: Enzymic and Nonenzymic Covalent Intermediates Kluger, Ronald; Tittmann, Kai Chemical Reviews, Vol. 108, Issue 6 https://doi.org/10.1021/cr068444m	journal	June 2008
Ionic Liquid-Mediated Formation of 5-Hydroxymethylfurfural—A Promising Biomass-Derived Building Block Zakrzewska, Małgorzata E.; Bogel-Łukasik, Ewa; Bogel-Łukasik, Rafał Chemical Reviews, Vol. 111, Issue 2, p. 397-417 https://doi.org/10.1021/cr100171a	journal	February 2011
Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources van Putten, Robert-Jan; van der Waal, Jan C.; de Jong, Ed Chemical Reviews, Vol. 113, Issue 3 https://doi.org/10.1021/cr300182k	journal	February 2013
Ionic Liquids and Their Interaction with Cellulose Pinkert, André; Marsh, Kenneth N.; Pang, Shusheng Chemical Reviews, Vol. 109, Issue 12 https://doi.org/10.1021/cr9001947	journal	December 2009
Solvent-Free Methods for Making Acetals Derived from Glycerol and Furfural and Their Use as a Biodiesel Fuel Component Wegenhart, Benjamin L.; Liu, Shuo; Thom, Melanie ACS Catalysis, Vol. 2, Issue 12 https://doi.org/10.1021/cs300562e	journal	October 2012
On the Mechanism of Thiamine Action. IV. ¹ Evidence from Studies on Model Systems Breslow, Ronald Journal of the American Chemical Society, Vol. 80, Issue 14 https://doi.org/10.1021/ja01547a064	journal	July 1958
RAPID DEUTERIUM EXCHANGE IN THIAZOLIUM SALTS ¹ Breslow, Ronald Journal of the American Chemical Society, Vol. 79, Issue 7 https://doi.org/10.1021/ja01564a064	journal	April 1957
The advent and development of organocatalysis MacMillan, David W. C. Nature, Vol. 455, Issue 7211 https://doi.org/10.1038/nature07367	journal	September 2008
The hydrodeoxygenation of bioderived furans into alkanes Sutton, Andrew D.; Waldie, Fraser D.; Wu, Ruilian Nature Chemistry, Vol. 5, Issue 5, p. 428-432 https://doi.org/10.1038/nchem.1609	journal	April 2013
Organocatalytic cascade reactions as a new tool in total synthesis Grondal, Christoph; Jeanty, Matthieu; Enders, Dieter Nature Chemistry, Vol. 2, Issue 3 https://doi.org/10.1038/nchem.539	journal	February 2010
Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy’s “Top 10” revisited Bozell, Joseph J.; Petersen, Gene R. Green Chemistry, Vol. 12, Issue 4, p. 539-554 https://doi.org/10.1039/b922014c	journal	January 2010
Towards the conversion of carbohydrate biomass feedstocks to biofuels via hydroxylmethylfurfural James, Olusola O.; Maity, Sudip; Usman, Lamidi Ajao Energy & Environmental Science, Vol. 3, Issue 12 https://doi.org/10.1039/b925869h	journal	January 2010
Catalytic conversion of biomass to biofuels Alonso, David Martin; Bond, Jesse Q.; Dumesic, James A. Green Chemistry, Vol. 12, Issue 9, p. 1493-1513 https://doi.org/10.1039/c004654j	journal	January 2010
5-Hydroxymethylfurfural (HMF) as a building block platform: Biological properties, synthesis and synthetic applications Rosatella, Andreia A.; Simeonov, Svilen P.; Frade, Raquel F. M. Green Chemistry, Vol. 13, Issue 4 https://doi.org/10.1039/c0gc00401d	journal	January 2011
Conversion of biomass to selected chemical products Gallezot, Pierre Chem. Soc. Rev., Vol. 41, Issue 4 https://doi.org/10.1039/c1cs15147a	journal	January 2012
Organocatalytic umpolung: N-heterocyclic carbenes and beyond Bugaut, Xavier; Glorius, Frank Chemical Society Reviews, Vol. 41, Issue 9 https://doi.org/10.1039/c2cs15333e	journal	January 2012
Production of high quality diesel from cellulose and hemicellulose by the Sylvan process: catalysts and process variables Corma, Avelino; de la Torre, Olalla; Renz, Michael Energy & Environmental Science, Vol. 5, Issue 4 https://doi.org/10.1039/c2ee02778j	journal	January 2012
Etherification and reductive etherification of 5-(hydroxymethyl)furfural: 5-(alkoxymethyl)furfurals and 2,5-bis(alkoxymethyl)furans as potential bio-diesel candidates Balakrishnan, Madhesan; Sacia, Eric R.; Bell, Alexis T. Green Chemistry, Vol. 14, Issue 6 https://doi.org/10.1039/c2gc35102a	journal	January 2012
Evolution of asymmetric organocatalysis: multi- and retrocatalysis Wende, Raffael C.; Schreiner, Peter R. Green Chemistry, Vol. 14, Issue 7 https://doi.org/10.1039/c2gc35160a	journal	January 2012
Organocatalytic upgrading of the key biorefining building block by a catalytic ionic liquid and N-heterocyclic carbenes Liu, Dajiang (D. J.); Zhang, Yuetao; Chen, Eugene Y.-X. Green Chemistry, Vol. 14, Issue 10, p. 2738-2746 https://doi.org/10.1039/c2gc36265a	journal	January 2012
Organocatalytic conversion of cellulose into a platform chemical Caes, Benjamin R.; Palte, Michael J.; Raines, Ronald T. Chem. Sci., Vol. 4, Issue 1 https://doi.org/10.1039/c2sc21403b	journal	January 2013
Gamma-valerolactone, a sustainable platform molecule derived from lignocellulosic biomass Alonso, David Martin; Wettstein, Stephanie G.; Dumesic, James A. Green Chemistry, Vol. 15, Issue 3 https://doi.org/10.1039/c3gc37065h	journal	January 2013
Hydroxymethylfurfural production from bioresources: past, present and future Teong, Siew Ping; Yi, Guangshun; Zhang, Yugen Green Chemistry, Vol. 16, Issue 4 https://doi.org/10.1039/c3gc42018c	journal	January 2014
Bisphenols from Furfurals by Organocatalysis and Gold Catalysis Hashmi, A. Stephen; Wölfle, Michael; Teles, J. Synlett, Vol. 2007, Issue 11, p. 1747-1752 https://doi.org/10.1055/s-2007-982569	journal	July 2007
Organocatalysis Jacobsen, E. N.; MacMillan, D. W. C. Proceedings of the National Academy of Sciences, Vol. 107, Issue 48 https://doi.org/10.1073/pnas.1016087107	journal	November 2010
An Efficient Nucleophilic Carbene Catalyst for the Asymmetric Benzoin Condensation Enders, Dieter; Kallfass, Ulrike Angewandte Chemie International Edition, Vol. 41, Issue 10 https://doi.org/10.1002/1521-3773(20020517)41:10<1743::AID-ANIE1743>3.0.CO;2-Q	journal	May 2002
Production of High-Quality Diesel from Biomass Waste Products Corma, Avelino; de la Torre, Olalla; Renz, Michael Angewandte Chemie International Edition, Vol. 50, Issue 10 https://doi.org/10.1002/anie.201007508	journal	January 2011
Catalysis in Ionic Liquids Pârvulescu, Vasile I.; Hardacre, Christopher Chemical Reviews, Vol. 107, Issue 6 https://doi.org/10.1021/cr050948h	journal	June 2007
Chemical Routes for the Transformation of Biomass into Chemicals Corma, Avelino; Iborra, Sara; Velty, Alexandra Chemical Reviews, Vol. 107, Issue 6, p. 2411-2502 https://doi.org/10.1021/cr050989d	journal	June 2007
Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering Huber, George W.; Iborra, Sara; Corma, Avelino Chemical Reviews, Vol. 106, Issue 9, p. 4044-4098 https://doi.org/10.1021/cr068360d	journal	September 2006
Solubility of Carbohydrates in Ionic Liquids Zakrzewska, Małgorzata Ewa; Bogel-Łukasik, Ewa; Bogel-Łukasik, Rafał Energy & Fuels, Vol. 24, Issue 2 https://doi.org/10.1021/ef901215m	journal	February 2010
Dissolution of Cellose with Ionic Liquids Swatloski, Richard P.; Spear, Scott K.; Holbrey, John D. Journal of the American Chemical Society, Vol. 124, Issue 18, p. 4974-4975 https://doi.org/10.1021/ja025790m	journal	May 2002
Biomass Conversion to High Value Chemicals: From Furfural to Chiral Hydrofuroins in Two Steps Kabro, Anzhelika; Escudero-Adán, Eduardo C.; Grushin, Vladimir V. Organic Letters, Vol. 14, Issue 15 https://doi.org/10.1021/ol3018402	journal	July 2012
Where are ionic liquid strategies most suited in the pursuit of chemicals and energy from lignocellulosic biomass? Sun, Ning; Rodríguez, Héctor; Rahman, Mustafizur Chem. Commun., Vol. 47, Issue 5 https://doi.org/10.1039/C0CC03990J	journal	January 2011
Conversion of biomass to selected chemical products Gallezot, Pierre Chem. Soc. Rev., Vol. 41, Issue 4 https://doi.org/10.1039/C1CS15147A	journal	January 2012
Organocatalytic conversion of cellulose into a platform chemical Caes, Benjamin R.; Palte, Michael J.; Raines, Ronald T. Chem. Sci., Vol. 4, Issue 1 https://doi.org/10.1039/C2SC21403B	journal	January 2013
Advances in 5-hydroxymethylfurfural production from biomass in biphasic solvents Saha, Basudeb; Abu-Omar, Mahdi M. Green Chem., Vol. 16, Issue 1 https://doi.org/10.1039/C3GC41324A	journal	January 2014
Catalytic dehydration of C ₆ carbohydrates for the production of hydroxymethylfurfural (HMF) as a versatile platform chemical Wang, Tianfu; Nolte, Michael W.; Shanks, Brent H. Green Chem., Vol. 16, Issue 2 https://doi.org/10.1039/C3GC41365A	journal	January 2014
Organocatalysis in biorefining for biomass conversion and upgrading Liu, Dajiang (D. J.); Chen, Eugene Y. -X. Green Chem., Vol. 16, Issue 3 https://doi.org/10.1039/C3GC41934G	journal	January 2014
Mechanism of cellulose dissolution in the ionic liquid 1-n-butyl-3-methylimidazolium chloride: a ¹³C and ^35/37Cl NMR relaxation study on model systems Remsing, Richard C.; Swatloski, Richard P.; Rogers, Robin D. Chemical Communications, Issue 12, 1271-1273 https://doi.org/10.1039/b600586c	journal	January 2006
Production of high quality fuels from lignocellulose-derived chemicals: a convenient C–C bond formation of furfural, 5-methylfurfural and aromatic aldehyde Huang, Yao-Bing; Yang, Zhen; Dai, Jian-Jun RSC Advances, Vol. 2, Issue 30, p. 11211-11214 https://doi.org/10.1039/c2ra22008c	journal	January 2012
Über die präparative Nutzung der Thiazoliumsalz-katalysierten Acyloin- und Benzoin-Bildung, I. Herstellung von einfachen Acyloinen und Benzoinen Stetter, Hermann; RÄMsch, René Yvonne; Kuhlmann, Heinrich Synthesis, Vol. 1976, Issue 11 https://doi.org/10.1055/s-1976-24177	journal	January 1976
Production of Liquid Alkanes by Aqueous-Phase Processing of Biomass-Derived Carbohydrates Huber, George W.; Chheda, Juben N.; Barrett, Christopher J. Science, Vol. 308, Issue 5727, p. 1446-1450 https://doi.org/10.1126/science.1111166	journal	June 2005

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Related Subjects

09 BIOMASS FUELS
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
5-hydroxymethyl furfural (HMF)
59 BASIC BIOLOGICAL SCIENCES
N-heterocyclic carbene
biomass
biorefining
furfural
ionic liquid
organocatalysis
umpolung coupling