Diesel and alkane fuels from biomass by organocatalysis and metal-acid tandem catalysis.

Combo deal: Biomass furaldehydes are upgraded into oxygenated diesel and high-quality C10-12 linear alkane fuels. The first of two steps involves solvent-free self-condensation (Umpolung) through organocatalysis using an N-heterocyclic carbene (NHC), yielding C10 -C12 furoin intermediates. In the metal-acid tandem catalysis step, in water, the furoin intermediates are converted into oxygenated biodiesel by hydrogenation, etherification or esterification; or into premium alkane jet fuels by hydrodeoxygenation.

[1]  F. Hahn,et al.  Heterocyclic carbenes: synthesis and coordination chemistry. , 2008, Angewandte Chemie.

[2]  D. Enders,et al.  Organocatalysis by N-heterocyclic carbenes. , 2007, Chemical reviews.

[3]  Mark Mascal,et al.  High-yield conversion of plant biomass into the key value-added feedstocks 5-(hydroxymethyl)furfural, levulinic acid, and levulinic esters via 5-(chloromethyl)furfural , 2010 .

[4]  Michael Stöcker,et al.  Bio‐ und BTL‐Kraftstoffe in der Bioraffinerie: katalytische Umwandlung Lignocellulose‐reicher Biomasse mit porösen Stoffen , 2008 .

[5]  F. Glorius,et al.  Das Maß aller Ringe – N‐heterocyclische Carbene , 2010 .

[6]  A. Lemonidou,et al.  Aqueous-phase hydrodeoxygenation of bio-derived phenols to cycloalkanes , 2011 .

[7]  Volkan Degirmenci,et al.  Glucose activation by transient Cr2+ dimers. , 2010, Angewandte Chemie.

[8]  Ronald Breslow,et al.  On the Mechanism of Thiamine Action. IV.1 Evidence from Studies on Model Systems , 1958 .

[9]  V. Nair,et al.  Recent advances in carbon-carbon bond-forming reactions involving homoenolates generated by NHC catalysis. , 2008, Chemical Society reviews.

[10]  Joseph B. Binder,et al.  Mechanistic insights on the conversion of sugars into 5-hydroxymethylfurfural , 2010 .

[11]  Dajiang Liu,et al.  Ubiquitous aluminum alkyls and alkoxides as effective catalysts for glucose to HMF conversion in ionic liquids , 2012 .

[12]  Dajiang Liu,et al.  Organocatalytic upgrading of the key biorefining building block by a catalytic ionic liquid and N-heterocyclic carbenes , 2012 .

[13]  C. Afonso,et al.  An integrated approach for the production and isolation of 5-hydroxymethylfurfural from carbohydrates. , 2012, ChemSusChem.

[14]  Ruilian Wu,et al.  The hydrodeoxygenation of bioderived furans into alkanes. , 2013, Nature chemistry.

[15]  István T. Horváth,et al.  Valorization of Biomass: Deriving More Value from Waste , 2012, Science.

[16]  O. O. James,et al.  Towards the conversion of carbohydrate biomass feedstocks to biofuels via hydroxylmethylfurfural , 2010 .

[17]  Chen Zhao,et al.  Selective Hydrodeoxygenation of Lignin‐Derived Phenolic Monomers and Dimers to Cycloalkanes on Pd/C and HZSM‐5 Catalysts , 2012 .

[18]  Wenjing Fu,et al.  Synthesis of 5-(hydroxymethyl)furfural in ionic liquids: paving the way to renewable chemicals. , 2011, ChemSusChem.

[19]  M. Kim,et al.  Benzoin condensation reactions of 5-membered heterocyclic compounds , 1992 .

[20]  G. Huber,et al.  Liquid-phase catalytic processing of biomass-derived oxygenated hydrocarbons to fuels and chemicals. , 2007, Angewandte Chemie.

[21]  Nicolas Marion,et al.  N-heterocyclic carbenes as organocatalysts. , 2007, Angewandte Chemie.

[22]  Ruilian Wu,et al.  Functional group dependence of the acid catalyzed ring opening of biomass derived furan rings: an experimental and theoretical study , 2013 .

[23]  R. Bogel-Łukasik,et al.  Ionic liquid-mediated formation of 5-hydroxymethylfurfural-a promising biomass-derived building block. , 2011, Chemical reviews.

[24]  Qian Wang,et al.  Catalytic conversion of carbohydrates into 5-hydroxymethylfurfural by germanium(IV) chloride in ionic liquids. , 2010, ChemSusChem.

[25]  F. Glorius,et al.  The measure of all rings--N-heterocyclic carbenes. , 2010, Angewandte Chemie.

[26]  Weiran Yang,et al.  Direct catalytic synthesis of 5-methylfurfural from biomass-derived carbohydrates. , 2011, ChemSusChem.

[27]  Ed de Jong,et al.  Hydroxymethylfurfural, a versatile platform chemical made from renewable resources. , 2013, Chemical reviews.

[28]  A. Corma,et al.  Chemical routes for the transformation of biomass into chemicals. , 2007, Chemical reviews.

[29]  Converting carbohydrates to bulk chemicals and fine chemicals over heterogeneous catalysts , 2011 .

[30]  R. Raines,et al.  Organocatalytic Conversion of Cellulose into a Platform Chemical. , 2013, Chemical science.

[31]  Joseph J. Bozell,et al.  Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy’s “Top 10” revisited , 2010 .

[32]  C. Afonso,et al.  5-Hydroxymethylfurfural (HMF) as a building block platform: Biological properties, synthesis and synthetic applications , 2011 .

[33]  Avelino Corma,et al.  Production of high-quality diesel from biomass waste products. , 2011, Angewandte Chemie.

[34]  M. Mascal,et al.  Direct, high-yield conversion of cellulose into biofuel. , 2008, Angewandte Chemie.

[35]  J. H. Teles,et al.  Umpolung mit N‐heterocyclischen Carbenen: Generierung und Reaktivität von Breslow‐Intermediaten (2,2‐Diaminoenole) , 2012 .

[36]  James A. Dumesic,et al.  Production of 5-Hydroxymethylfurfural from Glucose Using a Combination of Lewis and Brønsted Acid Catalysts in Water in a Biphasic Reactor with an Alkylphenol Solvent , 2012 .

[37]  A. Riisager,et al.  Metal-free dehydration of glucose to 5-(hydroxymethyl)furfural in ionic liquids with boric acid as a promoter. , 2011, Chemistry.

[38]  D. M. Alonso,et al.  Catalytic conversion of biomass to biofuels , 2010 .

[39]  Xinhua Qi,et al.  Fast transformation of glucose and di-/polysaccharides into 5-hydroxymethylfurfural by microwave heating in an ionic liquid/catalyst system. , 2010, ChemSusChem.

[40]  Johnathan E. Holladay,et al.  Metal Chlorides in Ionic Liquid Solvents Convert Sugars to 5-Hydroxymethylfurfural , 2007, Science.

[41]  Dajiang Liu,et al.  Polymeric ionic liquid (PIL)-supported recyclable catalysts for biomass conversion into HMF. , 2013 .

[42]  Mareike C. Jahnke,et al.  Heterocyclische Carbene – Synthese und Koordinationschemie , 2008 .

[43]  M. Abu‐Omar,et al.  Solvent-Free Methods for Making Acetals Derived from Glycerol and Furfural and Their Use as a Biodiesel Fuel Component , 2012 .

[44]  A. Hashmi,et al.  Bisphenols from Furfurals by Organocatalysis and Gold Catalysis , 2007 .

[45]  I. Kozhevnikov,et al.  Efficient hydrodeoxygenation of biomass-derived ketones over bifunctional Pt-polyoxometalate catalyst. , 2012, Chemical communications.

[46]  Chen Zhao,et al.  Upgrading pyrolysis oil over Ni/HZSM-5 by cascade reactions. , 2012, Angewandte Chemie.

[47]  Juben Nemchand Chheda,et al.  Katalytische Flüssigphasenumwandlung oxygenierter Kohlenwasserstoffe aus Biomasse zu Treibstoffen und Rohstoffen für die Chemiewirtschaft , 2007 .

[48]  Q. Guo,et al.  Production of high quality fuels from lignocellulose-derived chemicals: a convenient C–C bond formation of furfural , 5-methylfurfural and aromatic aldehyde , 2012 .

[49]  Xiaohong Wang,et al.  Hydrolysis of Cellulose over CsxH3–xPW12O40 (X = 1–3) Heteropoly Acid Catalysts , 2011 .

[50]  Michael Stöcker,et al.  Biofuels and biomass-to-liquid fuels in the biorefinery: catalytic conversion of lignocellulosic biomass using porous materials. , 2008, Angewandte Chemie.

[51]  G. Huber,et al.  Production of Liquid Alkanes by Aqueous-Phase Processing of Biomass-Derived Carbohydrates , 2005, Science.

[52]  Q. Zhang,et al.  A review of catalytic hydrodeoxygenation of lignin-derived phenols from biomass pyrolysis. , 2012, Bioresource technology.

[53]  N. Schlörer,et al.  Umpolung by N-heterocyclic carbenes: generation and reactivity of the elusive 2,2-diamino enols (Breslow intermediates). , 2012, Angewandte Chemie.

[54]  Ronald T. Raines,et al.  Simple chemical transformation of lignocellulosic biomass into furans for fuels and chemicals. , 2009, Journal of the American Chemical Society.

[55]  Jianghua He,et al.  Chromium(0) nanoparticles as effective catalyst for the conversion of glucose into 5-hydroxymethylfurfural. , 2013, ChemSusChem.

[56]  Nicolas Marion,et al.  N‐heterocyclische Carbene als Organokatalysatoren , 2007 .

[57]  Alexis T. Bell,et al.  Etherification and reductive etherification of 5-(hydroxymethyl)furfural: 5-(alkoxymethyl)furfurals and 2,5-bis(alkoxymethyl)furans as potential bio-diesel candidates , 2012 .

[58]  Dongke Zhang,et al.  A process for efficient conversion of fructose into 5-hydroxymethylfurfural in ammonium salts , 2011 .

[59]  A. Corma,et al.  Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering. , 2006, Chemical reviews.

[60]  Ruilian Wu,et al.  Comparison of Copper and Vanadium Homogeneous Catalysts for Aerobic Oxidation of Lignin Models , 2011 .