- Tailor-made biofuel 2-butyltetrahydrofuran from the continuous flow hydrogenation and deoxygenation of furfuralacetone
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In this work, we present the first continuous flow process to produce the tailored biofuel 2-butyltetrahydrofuran from renewable resources. In a two-step approach lignocellulose-derived furfuralacetone is first hydrogenated and then deoxygenated over commercial catalysts to form the desired product. Both reactions were studied independently in batch conditions. The transition to a continuous flow system was done and various parameters were tested in the miniplant. Both reactions were performed in a two-reactor-concept approach to yield the desired 2-butyltetrahydrofuran in a high yield directly from furfuralacetone.
- Strohmann, Marc,Bordet, Alexis,Vorholt, Andreas J.,Leitner, Walter
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supporting information
p. 6299 - 6306
(2019/12/03)
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- Solvent effects in hydrodeoxygenation of furfural-acetone aldol condensation products over Pt/TiO2 catalyst
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The solvent effects on hydrodeoxygenation (HDO) of 4-(2-furyl)-3-buten-2-one (F-Ac) over Pt/TiO2 catalyst were investigated at T = 200 °C and P(H2) = 50 bar. The initial reactant is the main product of aldol condensation between furfural and acetone, which constitutes a promising route for the production of bio-based chemicals and fuels. A sequence of experiments was performed using a selection of polar solvents with different chemical natures: protic (methanol, ethanol, 1-propanol, 2-propanol, 1-pentanol) and aprotic (acetone, tetrahydrofuran (THF), n,n-dimethylformamide (DMF)). In case of protic solvents, a good correlation was found between the polarity parameters and conversion. Consequently, the highest hydrogenation rate was observed when 2-propanol was used as a solvent. In contrast, the hydrogenation activity in presence of aprotic solvents was related rather to solvent-catalyst interactions. Thus, the initial hydrogenation rate declined in order Acetone > THF > DMF, i.e. in accordance with the increase in the nucleophilic donor number and solvent desorption energy. Regarding the product distribution, a complex mixture of intermediates was obtained, owing to the successive hydrogenation (aliphatic C[dbnd]C, furanic C[dbnd]C and ketonic C[dbnd]O bonds), ring opening (via C[sbnd]O hydrogenolysis) and deoxygenation reactions. Based on the proposed reaction scheme for the conversion of F-Ac into octane, the influence of the studied solvents over the cascade catalytic conversion is discussed. A significant formation of cyclic saturated compounds such as 2-propyl-tetrahydropyran and 2-methyl-1,6-dioxaspiro[4,4]nonane took place via undesirable side reactions of cyclization and isomerization. The best catalytic performance was found when using acetone and 2-propanol as solvents, achieving significant yields of 4-(2-tetrahydrofuryl)-butan-2-ol (28.5–40.4%) and linear alcohols (6.3–10.4%). The better performance of these solvents may be associated with a lower activation energy barrier for key intermediate products, due to their moderate interaction with the reactant and the catalyst. In case of methanol and DMF, undesired reactions between the reactant and the solvent took place, leading to a lower selectivity towards the targeted hydrodeoxygenated products.
- Ramos, Rubén,Ti?ler, Zdeněk,Kikhtyanin, Oleg,Kubi?ka, David
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p. 174 - 183
(2016/12/06)
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- Ammonium-salt-tagged IMesAuCl complexes and their application in gold-catalyzed cycloisomerization reactions in water
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The total synthesis and characterization of ammonium-salt-tagged IMesAuCl complexes is described. Moreover, we have demonstrated their catalytic activity and recyclability in cycloisomerization reactions of allenic and acetylenic alcohols in water. The water-soluble gold catalysts can be stabilized by the addition of LiCl.
- Belger, Katrin,Krause, Norbert
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p. 220 - 225
(2015/02/02)
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- Effective production of octane from biomass derivatives under mild conditions
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Cool cats dont feel pressure: Furfural is catalytically converted into octane in high yields at relatively low pressures and temperatures. In a three-step process, two bifunctional catalysts, Pt/Co2AlO4 and Pt/NbOPO4, play crucial roles in achieving C8-ols from 4-(2-furyl)-3-buten-2-one and transforming the C8-ols into octane, respectively.
- Xu, Wenjie,Xia, Qineng,Zhang, Yu,Guo, Yong,Wang, Yanqin,Lu, Guanzhong
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experimental part
p. 1758 - 1761
(2012/03/27)
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- Consecutive reactions with sulfoximines: Straightforward synthesis of substituted 5,5-spiroketals
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An efficient synthesis of 5,5-spiroketals (i.e., 1,6-dioxa-spiro[4.4]nonane derivatives) is described from 2-(sulfonimidoyl-methylene)tetrahydrofurans involving a consecutive epoxide opening/oxa-Michael spiroketalization sequence. This methodology was applied to the very direct synthesis of chalcogran, a beetle pheromone. Georg Thieme Verlag Stuttgart ? New York.
- Sridharan, Vellaisamy,Vologdin, Nikolay,Virolleaud, Marie-Alice,Bonne, Damien,Bressy, Cyril,Chouraqui, Gaelle,Commeiras, Laurent,Parrain, Jean-Luc,Coquerel, Yoann,Rodriguez, Jean
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p. 2085 - 2090
(2011/07/30)
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- Cooperativity in bimetallic dihydroalkoxylation catalysts built on aromatic scaffolds: Significant rate enhancements with a rigid anthracene scaffold
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This work describes investigations into metal-catalyzed sequential reactions using a series of single metal and bimetallic Rh(I) and/or Ir(I) pyrazolyl complexes. Monometallic complexes with bis(1-pyrazolyl)methane (bpm) ligands [M(CO)2(bpm)]BArF 4 (1), bimetallic complexes [M2(CO)2(Lscaffold)][BArF 4]2 (2-4) where M = Rh(I) or Ir(I) bearing bitopic ligands Lscaffold = bis(1-pyrazolyl)methane-derived ligands, p-C 6H4[CH(pz)2]2 (Lp), m-C6H4[CH(pz)2]2 (Lm), and anthracene-bridged 1,8-C14H8[CH(pz)2] 2 (LAnt), [M2(CO)4(L p)]-[BArF 4]2 (2), [M 2(CO)4(Lm)][BArF 4] 2 (3), and [M2(CO)4(LAnt)][BAr F 4]2 (4) were used as catalysts. The efficiency of the complexes as catalysts was tested for the dihydroalkoxylation of a series of alkyne diol substrates, 2-(6-hydroxyhex-1-ynyl)benzyl alcohol (5), 1-methyl-3-heptyne-1,7-diol (6), 2-(5-hydroxypent-1-ynyl)benzyl alcohol (7), and 2-(4-hydroxybut-1-ynyl)benzyl alcohol (8), forming spiroketals. All complexes tested were highly effective catalysts for the intramolecular dihydroalkoxylation reaction. The homobimetallic complexes 2-4 showed significant enhancement in activity and selectivity relative to the single metal catalysts (1). The order of catalytic activity of the bimetallic complexes was found to be [M2(CO)4(LAnt)][BArF 4]2 > [M2(CO)4(L m)][BArF 4]2 > [M 2(CO)4(Lp)][BArF 4] 2 for all substrates, and the bimetallic cooperativity index was established for each reaction.
- Ho, Joanne H. H.,Choy, Sandra W. S.,MacGregor, Stuart A.,Messerle, Barbara A.
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experimental part
p. 5978 - 5984
(2012/01/04)
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- A novel mesoporous Pd/cobalt aluminate bifunctional catalyst for aldol condensation and following hydrogenation
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A novel mesoporous Pd/cobalt aluminate bifunctional catalyst has been synthesized by a facile co-precipitation process and used in aldol condensation of furfural with acetone and the following hydrogenation of condensation products. This kind of bifunctional catalyst has good activity and can be recycled and regenerated easily. Crown Copyright
- Xu, Wenjie,Liu, Xiaohui,Ren, Jiawen,Zhang, Peng,Wang, Yanqin,Guo, Yanglong,Guo, Yun,Lu, Guanzhong
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experimental part
p. 721 - 726
(2010/07/06)
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- Highly efficient Rh(i) and Ir(i) single and dual metal catalysed dihydroalkoxylation reactions of alkyne diols
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A highly efficient rhodium(i) and iridium(i) catalysed dihydroalkoxylation reaction of alkyne diols is employed here for the synthesis of spiroketals and a fused bicyclic ketal. The two metal catalysts show differential selectivity and efficiency for either the cyclisation of the 5-exo or 6-endo-membered rings. For the first time, a dual metal (Rh and Ir) catalyst system is effectively utilised for the formation of the 5,6-spiroketals, more efficiently than the single metal catalysts. The two different metals create a dual activation pathway to enhance the 5- and 6-membered ring closure as compared with the equivalent single catalysts.
- Ho, Joanne Hui Hui,Hodgson, Richard,Wagler, Joerg,Messerle, Barbara Ann
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scheme or table
p. 4062 - 4069
(2010/06/18)
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- Highly efficient catalytic routes to spiroketal motifs
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The versatile and efficient synthesis of a variety of spiroketal motifs via the double intramolecular hydroalkoxylation of aliphatic and aromatic alkyne diols was achieved using simple and readily accessible Ir(I) and Rh(I) cyclooctadiene complexes as cat
- Selvaratnam, Selvasothi,Ho, Joanne H.H.,Huleatt, Paul B.,Messerle, Barbara A.,Chai, Christina L.L.
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scheme or table
p. 1125 - 1127
(2009/05/27)
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- Tellurium/lithium exchange reactions in the synthesis of spiroketals and 1,6-dioxygenated systems
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1,4-C,O-dianions have been generated through concomitant acid/base and tellurium/lithium exchange reactions. The di-lithium salts were transmetallated with cerium chloride to the corresponding di-cerium salts and subsequently reacted with lactones and carboxylic acid anhydrides to yield the respective spiroketals. The di-lithium entities were also converted into the corresponding cyanocuprates that add in a 1,4-manner to 2-cyclohexen-1-one to form 1,6-dioxygenated compounds.
- Dos Santos, Alcindo A.,Princival, Jefferson L.,Comasseto, Jo?o V.,de Barros, Simone M.G.,Neto, José E. Brainer
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p. 5167 - 5172
(2008/02/01)
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- Organoselenium mediated asymmetric cyclizations. Synthesis of enantiomerically pure 1,6-dioxaspiro[4.4]nonanes
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The asymmetric cyclization of 1-hydroxyoct-7-en-4-one, promoted by camphorselenenyl tetrafluoroborate, generated from camphor diselenide and silver tetrafluoroborate in dichloromethane at room temperature, afforded a mixture of two diastereoisomeric E- and two diastereoisomeric Z-2-[(camphorseleno)methyl]-1,6-dioxaspiro[4.4]nonanes. These were separated by medium pressure liquid chromatography and then deselenenylated with triphenyltin hydride and AIBN to give enantiomerically pure 2-methyl-1,6-dioxaspiro[4.4]nonanes. The camphorseleno group was also substituted by an allyl function using allyltributyltin in the presence of AIBN.
- Tiecco, Marcello,Testaferri, Lorenzo,Bagnoli, Luana,Scarponi, Catalina,Temperini, Andrea,Marini, Francesca,Santi, Claudio
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p. 2768 - 2774
(2007/10/03)
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- Alkynyltrifluoroborates as versatile tools in organic synthesis: A new route to spiroketals
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(Chemical Equation Presented) A simple and efficient two-step approach to spiroketals is described. Key steps include the preparation of functionalized hydroxyl α-alkynones by ring-opening reactions of lactones with lithium alkynyltrifluoroborates followed by a palladium-catalyzed hydrogenation/ spirocyclization of the prespiroketal intermediate.
- Doubsky, Jan,Streinz, Ludvik,Saman, David,Zednik, Jiri,Koutek, Bohumir
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p. 4909 - 4911
(2007/10/03)
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- Synthesis of spiroacetal pheromones via metalated hydrazones
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The synthesis of simple alkyl substituted spiroacetals by α,α'-alkylation of metalated acetone dimethylhydrazone with appropriate electrophiles and subsequent acid catalyzed cleavage and ring closure of the products is described.
- Enders,Dahmen,Dederichs,Gatzweiler,Weuster
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p. 1013 - 1019
(2007/10/02)
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- Synthesis of Spiroacetals using Organoselenium-mediated Cyclisation Reactions. X-Ray Molecular Structure of (2S,8R)-8-Methyl-2-phenyl-1,7-dioxaspiroundecan-4(R)-ol
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Alkenyl hydroxyketones undergo cyclisation via their hemiacetal form, in the presence of N-phenylselenophthalimide (NPSP) and a Lewis acid, to give the corresponding phenylseleno-substituted spiroacetals.Using this methodology the synthesis of trans- and cis-2-methyl-1,6-dioxaspirononane (1), trans- and cis-2-ethyl-1,6-dioxaspirononane (chalcogran)(2), trans- and cis-2-methyl-1,6-dioxaspirodecane(3), trans-7-methyl-1,6-dioxaspirodecane (4), trans-2-methyl-1,7-dioxaspiroundecane (5), and (2S,8R)-8-methyl-2-phenyl-1,7-dioxaspiroundecane-4-one(6) has been achieved, after reductive removal of selenium using Raney-nickel in diethyl ether.Compound (2) is the principal aggregation pheromone from Pityogenes chalcographus (L), whilst compounds (3) and (4) constitute the pheromone components of the common wasp, Paravespula vulgaris.The structure of the spiroacetal (6) was determined as a result of X-ray crystallography of a later derivative, obtained by sodium borohydride reduction of (6).
- Doherty, Annette M.,Ley, Steven V.,Lygo, Barry,Williams, David J.
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p. 1371 - 1378
(2007/10/02)
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- SPIROACETALS FROM ACETONE AND OXIRANES - A SIMPLE ROUTE TO OPTICALLY ACTIVE 1,6-DIOXASPIRONONANE-PHEROMONES
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A new and efficient synthesis of 1,6-dioxaspirononane-spiroacetals, starting from the simple building blocks acetone and oxiranes is described.
- Enders, D.,Dahmen, W.,Dederichs, E.,Weuster, P.
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p. 1235 - 1242
(2007/10/02)
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- 2,9-DIOXABICYCLONONAN-DARSTELLUNG, MASSENSPEKTROSKOPIE UND UMLAGERUNG EINES NEUEN HETEROCYCLISCHEN SYSTEMS
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Nine different methyl-substituted compounds of a new acetal system 5 are synthesized from 4-(5-methyl-2-furyl)alkanoles 1 and are rearranged to ketones 6; mass spectroscopic fragmentation patterns are described.
- Francke, Wittko,Reith, Wolfgang
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p. 2029 - 2032
(2007/10/02)
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- Useful Route to 1,6-Dioxaspirononane and 1,6-Dioxaspirodecane Derivatives
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A wide variety of derivatives of 1,6-dioxaspirononane and 1,6-dioxaspirodecane, including certain insect pheromones, can be conveniently prepared by reaction of the lithium salts of protected alkynols with equimolar amounts of lactones followed by hydrogenation and acid-catalyzed deprotection and cyclization.Alkynols are satisfactorily protected either as their tetrahydropyranyl or as their 1-ethoxyethyl ethers; intermediates need not be isolated.Yields are variable, but products are readily obtainable in high purity regardless of yield.
- Phillips, Catherine,Jacobson, Roy,Abrahams, Barbara,Williams, Howard J.,Smith, Leverett R.
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p. 1920 - 1924
(2007/10/02)
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