- Obtaining a high value branched bio-alkane from biomass-derived levulinic acid using RANEY as hydrodeoxygenation catalyst
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Compared to 5-HMF (C6H6O3), angelica lactone (C5H6O2) is a platform compound that has more potential for biomass-derived high performance bio-alkane fuel production due to a CC bond in the molecular structure, leading to a C-C coupling intermediate (C10 self-aggregation dimer) and higher C:O ratio (2.5), resulting in lower hydrogen consumption for the subsequent hydrodeoxygenation process. Biomass-derived levulinic acid was used as the only starting raw material to produce C10 branched alkanes. First, carboxyl and carbonyl functional groups of levulinic acid under catalysis via intramolecular esterification and dehydration yielded angelica lactone, which included two isomers of angelica lactone (α-angelica lactone and β-angelica lactone). Secondly, angelica lactone di/trimers would be obtained by angelica lactone self-aggregation: α-angelica lactone and β-angelica lactone connecting via C-C bond coupling. Finally, these intermediate products are selectively hydrodeoxygenated over a RANEY catalyst to obtain C7-C10 branched alkanes. Nearly a 90% yield can be achieved under 483 K and 5 MPa H2 and the C10 branched alkane product, 3-ethyl-4-methyl heptane, accounts for 75% of the same.
- Lu, Boqiong,Li, Jinlong,Lv, Guangqiang,Qi, Yongqin,Wang, Yingxiong,Deng, Tiansheng,Hou, Xianglin,Yang, Yongxing
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Read Online
- Synthesis of renewable diesel with 2-methylfuran and angelica lactone derived from carbohydrates
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Diesel and jet fuel range branched alkanes were first synthesized by the combination of hydroxyalkylation/alkylation (HAA) of 2-methylfuran with angelica lactone and subsequent hydrodeoxygenation. Compared with the previous ethyl levulinate route, the angelica lactone route exhibited evident advantages at higher HAA reactivity.
- Wang, Wei,Li, Ning,Li, Shanshan,Li, Guangyi,Chen, Fang,Sheng, Xueru,Wang, Aiqin,Wang, Xiaodong,Cong, Yu,Zhang, Tao
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- Regioselective β-Arylation of α-Angelica Lactone through Isomerization/Addition under Mild Conditions
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The conversion of biomass-based platform molecules into various high-value chemicals greatly promotes the utilization of renewable biomass resources. Herein, an example of Rh-catalyzed β-arylation of levulinic-acid-derived α-angelica lactone was reported, providing the γ-lactone-structure products with high regioselectivity. Both arylboronic and alkenylboronic acids could be applied in this transformation. This reaction tolerated a variety of synthetically important functional groups. Moreover, the obtained γ-lactone products could be readily converted to high-value products such as 1,4-diols and γ-methoxy-carboxylates.
- Zhuo, Kai-Feng,Yu, Shang-Hai,Gong, Tian-Jun,Fu, Yao
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- Synthesis of diastereo- and enantiomerically pure anti-3-methyl-1,4- pentanediol via lipase catalysed acylation
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Racemic trans-4,5-dimethylhydrofuran-2(3H)-one was synthesised from 5-methyl-furan-2(3H)-one, (α-angelica lactone). The key reaction in the synthesis was the 1,4-conjugate addition of an organocuprate to 5-methylfuran-2(5H)-one (β-angelica lactone). Different types of organocuprates were tested with the highest anti:syn ratio of 99.4:0.6 being obtained by the use of a Gilman organocuprate reagent. The enantioselective acylation of racemic 3-methyl-pentan-1,4-diol, catalysed by a variety of lipases in organic media, was investigated. The highest enantioselectivity (E >400) was obtained when Novozyme 435 was used as the catalyst at a water activity of aw ~ 0. Thus, both enantiomers, (3S,4R)- and (3R,4S)-3-methyl- pentan-1,4-diol, were obtained in very high diastereomeric (>99% de) and enantiomeric purities (>99.8% and >97.4% ee, respectively).
- Lindstroem, Mona,Hedenstroem, Erik,Bouilly, Sandrine,Velonia, Kelly,Smonou, Ioulia
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- Lewis-Pair-Mediated Selective Dimerization and Polymerization of Lignocellulose-Based β-Angelica Lactone into Biofuel and Acrylic Bioplastic
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This contribution reports an unprecedentedly efficient dimerization and the first successful polymerization of lignocellulose-based β-angelica lactone (β-AL) by utilizing a selective Lewis pair (LP) catalytic system, thereby establishing a versatile bio-refinery platform wherein two products, including a dimer for high-quality gasoline-like biofuel (C8–C9 branched alkanes, yield=87 %) and a heat- and solvent-resistant acrylic bioplastic (Mn up to 26.0 kg mol?1), can be synthesized from one feedstock by one catalytic system. The underlying reason for exquisite selectivity of the LP catalytic system toward dimerization and polymerization was explored mechanistically.
- Hong, Miao,Wang, Xiao-Jun
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supporting information
p. 2664 - 2668
(2020/01/24)
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- Biosynthesis of Pseudomonas-Derived Butenolides
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Butenolides are well-known signaling molecules in Gram-positive bacteria. Here, we describe a novel class of butenolides isolated from a Gram-negative Pseudomonas strain, the styrolides. Structure elucidation was aided by the total synthesis of styrolide A. Transposon mutagenesis enabled us to identify the styrolide biosynthetic gene cluster, and by using a homology search, we discovered the related and previously unknown acaterin biosynthetic gene cluster in another Pseudomonas species. Mutagenesis, heterologous expression, and identification of key shunt and intermediate products were crucial to propose a biosynthetic pathway for both Pseudomonas-derived butenolides. Comparative transcriptomics suggests a link between styrolide formation and the regulatory networks of the bacterium.
- Chowdhury, Somak,Klapper, Martin,Menzel, Klaus-Dieter,Paschold, André,Rosenbaum, Miriam A.,Schlabach, Kevin,Stallforth, Pierre,Zhang, Shuaibing
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supporting information
p. 5607 - 5610
(2020/02/04)
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- Scalable synthesis and polymerisation of a β-angelica lactone derived monomer
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Bio-based levulinic acid is easily ring-closed to α-angelica lactone (α-AL). α-AL can be isomerized to the conjugated β-AL under the influence of base, but since this is an equilibrium mixture it is very hard to devise a scalable process that would give pure β-AL. This problem was circumvented by distilling the equilibrium mixture to obtain a 90?:?10 mixture of β-and α-AL in 88% yield. This mixture was used for Diels-Alder reactions on 3 terpenes and on cyclopentadiene in up to 100 g scale. The latter DA adduct was subjected to a ROMP reaction catalysed by the Grubbs II catalyst. The resulting polymer has some similarities to poly-norbornene but is more polar. The polymer can be processed into films with very good transparency.
- De Vries, Johannes G.,Dell'Acqua, Andrea,Kirchhecker, Sarah,Stadler, Bernhard M.,Tin, Sergey
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supporting information
p. 5267 - 5273
(2020/09/17)
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- Cascade reaction engineering on zirconia-supported mesoporous MFI zeolites with tunable Lewis-Br?nsted acid sites: a case of the one-pot conversion of furfural to γ-valerolactone
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Catalytic cascade reactions are strongly desired as a potential means of combining multistep reactions into a single catalytic reactor. Appropriate catalysts composed of multi-reactive sites to catalyze cascade reactions in a sequential fashion are central to such efforts. Here, we demonstrate a bifunctional zeolite catalyst with close proximity of Br?nsted and Lewis acid sites through the synthesis of a mesoporous ZrO2[Al]MFI nanosponge (NS). The unique mesopores of the MFI-NS allow the confinement of zirconium oxide clusters (Lewis acid sites, LA) within the few-unit-cell-thin MFI aluminosilicate zeolite wall (Br?nsted acid sites, BA). Such a structure is clearly distinct from the conventional MFI zeolite, where the agglomeration of zirconium oxide clusters onto the external surface area within the crystal bulk is not possible, resulting in segregated BA and LA sites on the internal and external zeolite, respectively. By bringing the BA and LA within ZrO2[Al]MFI-NS 30, we uncovered a more efficient catalytic route for the conversion of furfural (100% within 2 h) to γ-valerolactone (GVL) (83%). This route is only evident when the long molecular diffusion path, in the most extreme case of physically mixed ZrO2-(LA) and Al-zeolites (BA) (45% of GVL yield), is eliminated. Unlike the bifunctional ZrO2-Al-beta (GVL yield of 75%), where the BA concentration is greatly compromised at the expense of LA formation, we also show that the ZrO2[Al]MFI-NS is able to maintain a high density and good stability of both types of acids.
- Huang, Jun,Kim, Jaeheon,Kim, Jeong-Chul,Kim, Kyung Duk,Ryoo, Ryong,Teoh, Wey Yang
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p. 35318 - 35328
(2020/10/19)
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- Conversion of levulinic acid to ethyl levulinate using tin modified silicotungstic acid supported on Ta2O5
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Tin modified silicotungstic acid (STA) deposited on Ta2O5 was explored as suitable catalyst for the conversion of levulinic acid to ethyl levulinate. The microwave synthesized catalysts of varying amounts of STA were characterised by N2 adsorption, powder XRD, FT-IR, FE-SEM, XPS, pyridine-FT-IR, TGA-DTA and NH3-TPD. Among the synthesized catalysts, 50% Sn2STA/Ta2O5 catalyst exhibited excellent catalytic activity for the esterification of levulinic acid providing 78% of ethyl levulinate yield and stable recyclability up to three cycles. The rate of esterification was 6.6 × 10?3 mol/g/min, which is significantly higher compared to reported values in the open literature. Mechanistic investigations revealed that the high catalytic activity was influenced by the presence of appropriate Br?nsted acid sites, surface area and porosity.
- Ganji, Parameswaram,Roy, Sounak
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- A facile synthesis of γ-butenolides via cyclization of 3-alkenoic acids with dimethyl sulfoxide and oxalyl bromide
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The combination of dimethyl sulfoxide and oxalyl bromide was used to accomplish the cyclization of 3-alkenoic acids with the aid of a base to afford γ-butenolides, in which bromodimethylsulfonium salt generated in situ was proposed to serve as a Br+ source.
- Ding, Rui,Liu, Yongguo,Liu, Lei,Li, Huimin,Tao, Sichen,Sun, Baoguo,Tian, Hongyu
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supporting information
p. 3001 - 3007
(2019/08/26)
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- A combo Zr-HY and Al-HY zeolite catalysts for the one-pot cascade transformation of biomass-derived furfural to Γ-valerolactone
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A highly efficient catalyst system was developed for the one-pot transformation of furfural to γ-valerolactone (GVL) in an open system. The cascade of two Meerwein Ponndorf Verley (MPV) reductions, ring-opening and esterification reactions was catalyzed by a physical mixture of Zr- and Al-HY zeolites where the proportion and strength of Lewis and Br?nsted acid sites could be independently optimized. The excellent activity of Zr-HY zeolites for the MPV reduction of furfural and levulinate ester with 2-pentanol as hydrogen donor was attributed to the larger pore size of HY-zeolites and stronger Lewis acidic sites compared to Zr-Beta. Al-HY zeolites were more effective as Br?nsted acid than Al-Beta because they converted furfuryl ether to levulinate ester rather than to β-angelica lactone. The dual catalytic system comprising Zr-HY (Si/Zr 20) and Al-HY (Si/Al 6) exhibited remarkably high catalytic activity with GVL yields of 85% after only 5 h at 120 °C.
- Zhang, Hongwei,Yang, Weijia,Roslan, Irwan Iskandar,Jaenicke, Stephan,Chuah, Gaik-Khuan
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- Selective Levulinic Acid Hydrogenation in the Presence of Hybrid Dendrimer-Based Catalysts. Part I: Monometallic
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Hybrid Ru-containing catalysts, based on poly(propylene imine) (PPI) dendrimers, immobilized in silica pores, were synthesized and characterized by transmission electron microscopy and X-ray photoelectron spectroscopy. The synthesized Ru catalysts proved their efficiency in the selective hydrogenation of levulinic acid and its esters at 80 °C, 30 bar of H2, and 50 % volume substrate concentration in water. Quantitative yields of γ-valerolactone were obtained for both micro- and mesoporous Ru catalysts within 2 h with catalytic activity as high as 1610 h?1. The reaction rate and selectivity on γ-valerolactone were found to depend on several factors such as carrier structure, temperature, presence of water, and substrate/Ru ratio. The novelty of these hybrid materials is the presence of both weak acid (SiO2) and organic base centers (dendrimer amino groups), enhancing the dispersion of Ru nanoparticles. The presence of amino groups in the catalyst stabilizes the Ru nanoparticles during the synthesis and promotes the adsorption of levulinic acid on the surface of Ru nanoparticles during the reaction. Synthesized hybrid Ru catalysts can be reused several times without significant loss of activity.
- Maximov, Anton L.,Zolotukhina, Anna V.,Mamedli, Adila A.,Kulikov, Leonid A.,Karakhanov, Edward A.
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p. 222 - 233
(2017/11/27)
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- Preparation of valeric acid and valerate esters from biomass-derived levulinic acid using metal triflates + Pd/C
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Recently, great attention has been paid to the study of the conversion of biomass-derived compounds to value-Added chemicals. Levulinic acid (LA) is a versatile and valuable chemical and its various applications have been described. The selective conversion of biomass-derived LA to produce valeric acid and valerate esters was successfully performed in the presence of H2, in which metal triflates and Pd/C were used as the catalysts. Under optimal conditions, a 99% conversion of LA and a 92% selectivity of valeric acid was obtained with Hf(OTf)4 and Pd/C as the catalysts at a relatively low temperature of 150 °C. Moreover, the metal center of the catalyst, the solvent, the reaction temperature and other reaction conditions were studied. In addition, the results of the recycling experiment exhibited that the catalysts continued to have a satisfactory activity after being reused 5 times.
- Zhou, Jian,Zhu, Rui,Deng, Jin,Fu, Yao
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p. 3974 - 3980
(2018/09/11)
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- Preparation method of alpha, beta-unsaturated-gamma-lactone
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The invention relates to a preparation method of alpha, beta-unsaturated-gamma-lactone shown as a structural formula below. The preparation method comprises the following steps: firstly dropwise adding a dichloromethane solution of dimethylsulfoxide (1.5 equiv) into a dichloromethane solution of oxaloyl bromide (1.5 equiv) at a temperature of 10 DEG C below zero, dropwise adding raw material (E) 3-alkenoic acid, then returning to a room temperature for reaction, adding a potassium carbonate aqueous solution and continuously reacting to obtain the corresponding alpha, beta-unsaturated-gamma-lactone; the yield is 85-90 percent.
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Paragraph 0005; 0012; 0013
(2018/09/08)
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- A Novel Method for the Chlorolactonization of Alkenoic Acids Using Diphenyl Sulfoxide/Oxalyl Chloride
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A facile chlorolactonization of alkenoic acids by treatment with diphenyl sulfoxide/oxalyl chloride has been developed. The reaction can generate various chlorolactones in moderate to good yields, wherein the chlorodiphenylsufonium salt derived from diphenyl sulfoxide/oxalyl chloride serves as the source of Cl +.
- Ding, Rui,Lan, Liyuan,Li, Shuhui,Liu, Yongguo,Yang, Shaoxiang,Tian, Hongyu,Sun, Baoguo
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p. 2555 - 2566
(2018/05/03)
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- Guiding a divergent reaction by photochemical control: Bichromatic selective access to levulinates and butenolides
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Allylic and acrylic substrates may be efficiently transformed by a sequential bichromatic photochemical process into derivatives of levulinates or butenolides with high selectivity when phenanthrene is used as a regulator. Thus, UV-A photoinduced cross-metathesis (CM) couples the acrylic and allylic counterparts and subsequent UV-C irradiation initiates E-Z isomerization of the carbon-carbon double bond, followed by one of two competing processes; namely, cyclization by transesterification or a 1,5-H shift and tautomerization. Quantum chemical calculations demonstrate that intermediates are strongly blue-shifted for the cyclization while red-shifted for the 1,5-H shift reaction. Hence, delaying the double bond migration by employing UV-C absorbing phenanthrene, results in a selective novel divergent all-photochemical pathway for the synthesis of fundamental structural motifs of ubiquitous natural products.
- Sutar, Revannath L.,Sen, Saumik,Eivgi, Or,Segalovich, Gal,Schapiro, Igor,Reany, Ofer,Lemcoff, N. Gabriel
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p. 1368 - 1374
(2018/02/09)
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- Catalytic upgrading of furfuryl alcohol to bio-products: Catalysts screening and kinetic analysis
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The conversion of furfuryl alcohol, a highly versatile biomass-derived platform molecule, into a large variety of bio-products, including ethers, lactones and levulinates, has been evaluated in alcohol media using different solid acid catalysts, such as commercial zeolites, sulfonic acid-functionalized materials, and sulfated zirconia. Reaction pathways and mechanisms have been correlated to the particular type of catalyst used, aiming to establish the influence of the main physico-chemical properties of the materials on the extent of furfuryl alcohol conversion, as well as on the predominant reaction pathway followed. Mechanistic and kinetics modelling studies for each type of catalyst have been developed and compared, providing an useful tool for the selection of the most suitable solid acid catalyst for the production of each of the reaction intermediates in the cascade from furfuryl alcohol to alkyl levulinate.
- Paniagua,Melero,Iglesias,Morales,Hernández,López-Aguado
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- Method for preparing alpha,beta-unsaturated gamma-lactone
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The invention relates to a method for preparing alpha,beta-unsaturated gamma-lactone represented by structural formula shown in the description. The method comprises the following steps: dropwise adding a dichloromethane solution of diphenyl sulfoxide (1.5 eq) to a dichloromethane solution of oxalyl chloride (1.5 eq) (or oxalyl bromide (1.5 eq)) at -78 DEG C, dropwise adding a raw material (E)-3-alkenoic acid, adding potassium carbonate and 18-crown-6 ether, and carrying out room temperature reaction to obtain the corresponding alpha,beta-unsaturated gamma-lactone with the yield of 80-85%.
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Paragraph 0010-0011; 0014-0015
(2018/01/09)
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- Effect of SiO2 support properties on the performance of Cu-SiO2 catalysts for the hydrogenation of levulinic acid to gamma valerolactone using formic acid as a hydrogen source
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Vapor phase catalytic transfer hydrogenation of aqueous levulinic acid (LA) with formic acid (FA) as a hydrogen source was carried out over copper loaded on to several SiO2 supports having different physicochemical properties. The SiO2 supports and Cu-SiO2 catalysts with different support properties were characterized by XRD, TPR, XPS, NH3-TPD and UV-vis techniques to evaluate the copper species and its interaction with the support. The SiO2 support alone showed lower LA conversion and low selectivity to GVL whereas Cu-SiO2 catalysts were found to show high conversion and selectivity to the desired product with formic acid as the hydrogen source. The difference in the activities and product selectivity among different copper supported silica appears to be a complex function of acidity and the nature of copper species in the Cu-SiO2 catalysts. No direct correlation was observed between a specific catalyst property such as acidity and pore size, and the performance of the Cu-SiO2 catalysts. From the characterization, it appears that the species responsible for higher activity and selectivity to GVL are monomeric partially oxidized copper species in a strong interaction with the support in combination with a higher number of acid sites, both of which are present in Cu-SiO2-Q6. Cu-SiO2-Q6 showed the highest conversion and selectivity of 66 and 81%, respectively, under optimized conditions.
- Lomate, Samadhan,Sultana, Asima,Fujitani, Tadahiro
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p. 3073 - 3083
(2017/08/15)
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- Metal-exchanged magnetic β-zeolites: Valorization of lignocellulosic biomass-derived compounds to platform chemicals
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An array of magnetically recoverable β-zeolites exchanged with late transition metals (Pd, Fe and Ir) have been synthesized and fully characterized and had their catalytic activity evaluated on the conversion of several bio-derived compounds to other value-added platform chemicals. The nature of the transition metals exchanged in the zeolite matrix and the significant effect of reaction conditions such as temperature, time and solvent usage on both the conversion and selectivity of the process are delineated.
- Jorge, Erlen Y. C.,Lima, Thiago De M.,Lima, Carolina G. S.,Marchini, Lucas,Castelblanco, William N.,Rivera, Daniel G.,Urquieta-González, Ernesto A.,Varma, Rajender S.,Paix?o, Márcio W.
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supporting information
p. 3856 - 3868
(2017/08/22)
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- Efficient formation of angelica lactones in a vapor-phase conversion of levulinic acid
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Vapor-phase lactonization of levulinic acid to produce angelica lactones, which include α-, β- and γ-form isomers, was performed in fixed-bed down-flow glass reactors over various oxide catalysts. SiO2 and SiO2-Al2O3 showed relatively high catalytic activity. The lactonization of levulinic acid to angelica lactones was found to be an endothermic equilibrium reaction, and the pressure equilibrium constant was calculated to be 0.2?atm at 275?°C. High temperatures and reduced pressures were effective for shifting the equilibrium from levulinic acid to angelica lactones, while the suitable reaction temperature was estimated to be 275?°C because temperatures higher than 275?°C decreased the selectivity to angelica lactones. The highest angelica lactones yield of 87.5% was achieved at a levulinic acid conversion of 95.3% over SiO2 under reduced pressure conditions of ca. 5?kPa at 275?°C. IR, NH3-TPD and TG analyses were performed for characterizing the catalysts used after the reactions together with a silylated SiO2 prepared for studying the active species on SiO2. The silanol groups of SiO2 with weak acidity were proposed to be the active species.
- Sun, Daolai,Takahashi, Yuta,Yamada, Yasuhiro,Sato, Satoshi
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- Subtle temperature-induced changes in small molecule conformer dynamics-observed and quantified by NOE spectroscopy
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NOE-distance relationships are shown to be sufficiently accurate to monitor very small changes in conformer populations in response to temperature (0.5%/10 °C)-in good agreement with Boltzmann-predictions, illustrating the effectiveness of accurate NOE-distance measurements in obtaining high quality dynamics as well as structural information for small molecules.
- Jones,Greenhalgh,Bame,Simpson,Cox,Marshall,Butts
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supporting information
p. 2920 - 2923
(2016/02/19)
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- Sequential Enzymatic Conversion of α-Angelica Lactone to γ-Valerolactone through Hydride-Independent C=C Bond Isomerization
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A case of hydride-independent reaction catalyzed by flavin-dependent ene-reductases from the Old Yellow Enzyme (OYE) family was identified. α-Angelica lactone was isomerized to the conjugated β-isomer in a nicotinamide-free and hydride-independent process. The catalytic cycle of C=C bond isomerization appears to be flavin-independent and to rely solely on a deprotonation–reprotonation sequence through acid–base catalysis. Key residues in the enzyme active site were mutated and provided insight on important mechanistic features. The isomerization of α-angelica lactone by OYE2 in aqueous buffer furnished 6.3 mm β-isomer in 15 min at 30 °C. In presence of nicotinamide adenine dinucleotide (NADH), the latter could be further reduced to γ-valerolactone. This enzymatic tool was successfully applied on semi-preparative scale and constitutes a sustainable process for the valorization of platform chemicals from renewable resources.
- Turrini, Nikolaus G.,Eger, Elisabeth,Reiter, Tamara C.,Faber, Kurt,Hall, Mélanie
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p. 3393 - 3396
(2016/12/27)
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- Low temperature hydrogenation of α-angelica lactone on silica supported Pd-NiO catalysts with synergistic effect
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The hydrogenation of α-angelica lactone (α-AL) was achieved under mild conditions on silica supported Pd-NiO catalysts. NiO and palladium were sequentially loaded on silica by wet-impregnation and deposition-reduction, respectively. First a series of NiO/SiO2 supports with varying Ni contents were prepared by a wet-impregnation method with Ni(NO3)2 as the precursor followed by calcination in air. Then a minute amount of palladium (0.2 wt%) was loaded by a deposition-reduction method using NaBH4 as a reducing reagent. The Pd-NiO catalysts were characterized by nitrogen adsorption, XRD, H2-TPR, XPS and TEM. The NiO were heterogeneously dispersed on silica with particle sizes ranging from 10 to 50 nm, whereas Pd was finely loaded with a diameter less than 5 nm. Nanoscale intimacy between Pd and NiO was noticed by HRTEM, resulting in high catalytic activity in liquid phase hydrogenation of α-angelica lactone to γ-valero lactone (GVL) under mild conditions. 0.2Pd-9.9NiO/SiO2 showed the best activity among all the catalysts investigated, with 82% conversion and 100% selectivity to GVL within several minutes at 30 °C and 0.3-1 MPa H2 pressure.
- Zhang, Pei,Yuan, Qingqing,Chen, Li,Xue, Teng,Guan, Yejun,Wu, Peng
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p. 65377 - 65382
(2016/07/26)
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- Catalytic oxidative C-C bond cleavage route of levulinic acid and methyl levulinate
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Recently, obtaining value-added chemicals from biomass resources has attracted considerable attention. Levulinic acid is one of the most important biomass platform compounds, which could be obtained from carbohydrate biomass. In this work, levulinic acid was selectively converted into C4 product, including succinic anhydride, via catalytic oxidation with a manganese catalyst in acetic anhydride. Moreover, an unexpected product of maleic anhydride was obtained, which greatly differs from that of levulinate ester. The pathway for formation of maleic anhydride was studied by monitoring and confirming intermediates α-angelica lactone and its derivative 2-methyl-5-oxotetrahydro-2-furanyl acetate. Based on the obtained mechanistic information, the different behaviour between the oxidative cleavage of levulinic acid and levulinate ester was further discussed.
- Xia, Fei,Du, Zhongtian,Liu, Junxia,Ma, Yangyang,Xu, Jie
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p. 72744 - 72749
(2016/08/09)
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- GASOLINE PREPARED FROM BIOMASS-DERIVED LEVULINIC ACID
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The present invention provides methods for preparing a C6-C10 alkane, and mixture thereof. The methods include forming a reaction mixture containing an angelica lactone dimer, a catalyst, and a hydrogen source under conditions sufficient to reduce the angelica lactone dimer, thereby preparing the alkane. The methods can be used to prepare branched alkanes useful for fuels. Methods for preparing an angelica lactone, methods for preparing an angelica lactone dimer, and methods for reducing a lactone to an alkane are also described.
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Paragraph 0076
(2015/06/03)
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- Catalytic Cross-Coupling of Vinyl Golds with Diazonium Salts under Photoredox and Thermal Conditions
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Catalytically generated vinyl gold complexes from tert-butyl allenoates were found to undergo an efficient cross-coupling with arenediazonium salts. The gold(I)-gold(III) redox cycle can be accessed under two different conditions, i.e., visible-light photoredox as well as a thermally induced radical chain pathway. The current C(sp2)-C(sp2) cross-coupling protocol that is catalytic in gold, would make available desirable structural diversity to the traditional cross-coupling chemistry.
- Patil, Dilip V.,Yun, Hokeun,Shin, Senghoon
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supporting information
p. 2622 - 2628
(2015/09/01)
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- Formation of C-C bonds for the production of bio-alkanes under mild conditions
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It is of crucial importance to form C-C bonds between biomass-derived compounds for the production of bio-alkanes from biomass. In this study, it was found that C-C bonds can be formed between angelica lactones, key intermediates derived from biomass, through free radical reactions under mild conditions without using a noble catalyst or solvent, which gave elongated carbon chains of di/trimers with 10 or 15 carbons, with complete conversion and 100% selectivity. The di/trimers produced serve as a novel feedstock for the carbon backbones of bio-alkanes. Hydrogenation of the di/trimers produced C6-C13 hydrocarbons suitable for use as transportation fuels. This journal is the Partner Organisations 2014.
- Xin, Jiayu,Zhang, Suojiang,Yan, Dongxia,Ayodele, Olubunmi,Lu, Xingmei,Wang, Jianji
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p. 3589 - 3595
(2014/07/08)
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- Hydrodeoxygenation of the angelica lactone dimer, a cellulose-based feedstock: Simple, high-yield synthesis of branched C7-C10 gasoline-like hydrocarbons
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Dehydration of biomass-derived levulinic acid under solid acid catalysis and treatment of the resulting angelica lactone with catalytic K 2CO3 produces the angelica lactone dimer in excellent yield. This dimer serves as a novel feedstock for hydrodeoxygenation, which proceeds under relatively mild conditions with a combination of oxophilic metal and noble metal catalysts to yield branched C7-C10 hydrocarbons in the gasoline volatility range. Considering that levulinic acid is available in >80 % conversion from raw biomass, a field-to-tank yield of drop-in, cellulosic gasoline of >60 % is possible. Fuel for thought: Biomass-derived levulinic acid can be converted in three simple steps via the angelica lactone dimer into branched, gasoline-range hydrocarbons in high yield by using a combination of oxophilic metal and noble metal catalysts (see scheme). Copyright
- Mascal, Mark,Dutta, Saikat,Gandarias, Inaki
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supporting information
p. 1854 - 1857
(2014/03/21)
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- Efficient, solvent-free hydrogenation of α-angelica lactone catalysed by Ru/C at atmospheric pressure and room temperature
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The hydrogenation of α-angelica lactone was investigated over Ru/C. A mild protocol was developed, which resulted in full conversion and 96% selectivity toward γ-valerolactone. The reaction network was investigated and α-angelica lactone was employed in the one-pot conversion into 2-methyltetrahydrofuran, demonstrating its superiority as a platform molecule in potential biorefinery schemes. This journal is the Partner Organisations 2014.
- Al-Shaal, Mohammad G.,Hausoul, Peter J. C.,Palkovits, Regina
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supporting information
p. 10206 - 10209
(2014/08/18)
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- Lewis base-catalyzed electrophilic lactonization of selenyl bromide resin and facile solid-phase synthesis of furan-2(5H)-one derivatives
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A facile solid-phase synthesis approach was developed for the rapid synthesis of multi-substituted furan-2(5H)-one derivatives libraries. The synthetic strategy included the selenyl bromide resin-induced electrophilic lactonization catalyzed by Lewis base, lithiation, nucleophilic substitution and oxidation-elimination of the selenium resins. The advantages of the new method are good yields, high purity, straightforward operations and high diversity of the products, lack of odor, and good stability of the selenium resins. Copyright
- Jun He, Rong,Chun Zhu, Bing,Wang, Yu Guang
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p. 523 - 528
(2014/07/07)
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- Domino reaction catalyzed by zeolites with Br?nsted and Lewis acid sites for the production of γ-valerolactone from furfural
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Take the straight path: Furfural was converted into γ-valerolactone (GVL) through sequential transfer-hydrogenation and hydrolysis reactions catalyzed by zeolites with Lewis and Br?nsted acid sites (see picture). Together, Zr-Beta and Al-MFI nanosheets generated GVL in 78 % yield without the use of precious metals or molecular H2. This system offers an attractive streamlined strategy for the production of GVL from biomass-derived molecules. Copyright
- Bui, Linh,Luo, Helen,Gunther, William R.,Román-Leshkov, Yuriy
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supporting information
p. 8022 - 8025
(2013/08/23)
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- Catalytic dehydration of d-xylose to 2-furfuraldehyde in the presence of Zr-(W,Al) mixed oxides. Tracing by-products using two-dimensional gas chromatography-time-of-flight mass spectrometry
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Zirconium-tungsten mixed oxides (ZrW) are effective catalysts in the aqueous-phase dehydration of d-xylose to 2-furfuraldehyde (Fur), at 170 °C. The texture and acid properties of ZrW materials were modified to enhance Fur yields. The catalysts prepared by co-condensation without a templating agent (ZrW(X), X = NO3, Cl; X is related to the type of zirconium precursor) possess relatively low specific surface area and amounts of accessible acid sites, leading to a modest Fur yield of ca. 35% at 99% conversion. The use of a templating agent in the preparation of mesoporous ZrW (ZrW-MP) increased considerably the specific surface area and the amount of accessible acid sites, which resulted in enhanced Fur yields (42%) reached at comparable conversions. Further improvements in Fur yields at high conversions were accomplished by introducing aluminium in the catalyst preparation procedure to give ZrAlW-MP (51% yield at 98% conversion). Fairly good catalytic results were also obtained in the case of the ZrAlW-MP catalyst, using solely water as solvent (46% yield at 93% conversion). A study of the identification of the reaction by-products by two-dimensional gas chromatography (GC × GC) combined with time-of-flight mass spectrometry (ToFMS) was carried out.
- Antunes, Margarida M.,Lima, Sérgio,Fernandes, Auguste,Candeias, Joana,Pillinger, Martyn,Rocha, Sílvia M.,Ribeiro, Maria Filipa,Valente, Anabela A.
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p. 127 - 135
(2013/01/15)
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- Asymmetric olefin isomerization of butenolides via proton transfer catalysis by an organic molecule
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An unprecedented enantioselective and general olefin isomerization was realized via biomimetic proton transfer catalysis with a new chiral organic catalyst. A broad range of mono- and disubstituted β,γ-unsaturated butenolides were transformed into the corresponding chiral α,β- unsaturated butenolides in high enantioselectivity and yield in the presence of as low as 0.5 mol % catalyst. Mechanistic studies have revealed the protonation as the rate-determining step.
- Wu, Yongwei,Singh, Ravi P.,Deng, Li
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supporting information; experimental part
p. 12458 - 12461
(2011/10/09)
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- Convenient synthesis of 5-alkylfuran-2(5H)-ones
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A convenient synthesis of 5-alkylfuran-2(5H)-ones are described starting from 3-nitropropanoate and aldehydes, promoted by neutral alumina, in 35-60% overall yields, via a condensation-lactonization-elimination pathway. Copyright
- Ma, Jie,Wang, Si Hong,Yin, Yan Bing
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p. 3026 - 3031
(2011/08/22)
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- Pd-catalyzed 5-endo-trig-type cyclization of β,γ-unsaturated carbonyl compounds: An efficient ring closing reaction to give γ-butenolides and 3-pyrrolin-2-ones
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The 5-endo-trig-type cyclization has been performed using a Pd-bis(isoxazoline) catalyst. The present cyclization of β,γ- unsaturated carbonyl compounds gave γ-butenolides and 3-pyrrolin-2-ones in good to excellent yields.
- Bajracharya, Gan B.,Koranne, Priti S.,Nadaf, Rashid N.,Gabr, Randa Kassem Mohamed,Takenaka, Kazuhiro,Takizawa, Shinobu,Sasai, Hiroaki
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supporting information; experimental part
p. 9064 - 9066
(2011/02/16)
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- γ-valerolactone ring-opening and decarboxylation over SiO 2/Al2O3 in the presence of water
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γ-Valerolactone (GVL) has been identified as a promising, sustainable platform molecule that can be produced from lignocellulosic biomass. The chemical flexibility of GVL has allowed the development of a variety of processes to prepare renewable fuels and chemicals. In the present work involving a combination of computational and experimental studies, we explore the factors governing the ring-opening of GVL to produce pentenoic acid isomers, as well as their subsequent decarboxylation over acid catalysts or hydrogenation over metal catalysts. The ring-opening of GVL has shown to be a reversible reaction, while both the decarboxylation and hydrogenation reactions are irreversible and kinetically controlled under the conditions studied (temperatures from about 500 to 650 K). The most significant contributor to lactone reactivity toward ring-opening is the size of the ring, with γ- lactones being more stable and less readily opened than δ- and ε-analogues. We have observed that the presence of either a C=C double bond or a lactone (which opens to form a C=C double bond) is necessary for appreciable rates of decarboxylation to occur. Olefinic acids exhibit higher rates of decarboxylation than the corresponding lactones, suggesting that the decarboxylation of alkene acids provides a lower energy pathway to olefin production than the direct decarboxylation of lactones. We observe lower rates of decarboxylation as the chain length of alkene acids increases; however, acrylic acid (3-carbon atoms) does not undergo decarboxylation at the conditions tested. These observations suggest that particular double bond configurations yield the highest rates of decarboxylation. Specifically, we suggest that the formation of a secondary carbenium ion in the β position leads to high reactivity for decarboxylation. Such an intermediate can be formed from 2- or 3-alkene acids which have at least four carbon atoms.
- Bond, Jesse Q.,Martin Alonso, David,West, Ryan M.,Dumesic, James A.
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experimental part
p. 16291 - 16298
(2011/12/02)
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- Tellurium in organic synthesis: synthesis of bioactive butenolides
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Reduction of (Z)-β-butyltelluro-enones gives the corresponding γ-hydroxy vinylic tellurides with retention of the double bond configuration. Reaction of γ-hydroxy vinylic tellurides with 2 equiv of n-butyllithium produces 1,4-C,O-dianions, which on reaction with carbon dioxide give the corresponding butenolides.
- Bassora, Bruno K.,Da Costa, Carlos E.,Gariani, Rogério A.,Comasseto, Jo?o V.,Dos Santos, Alcindo A.
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p. 1485 - 1487
(2008/02/02)
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- HYDROGENATION PROCESS FOR THE CONVERSION OF A CARBOXYLIC ACID OR AN ESTER HAVING A CARBONYL GROUP
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A hydrogenation process for the conversion of a reactant selected from the group consisting of a carboxylic acid having a carbonyl group and an ester of a carboxylic acid having a carbonyl group to form a carboxylic acid or an ester with a hydroxyl group or a lactone, wherein the reactant is contacted with a heterogeneous catalyst comprising a hydrogenating compound, in the presence of formic acid, at a temperature in the range of from 150 to 400° C. and a pressure in the range of from 1.0 to 150 bar (absolute).
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Page/Page column 3
(2008/06/13)
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- One-pot synthesis of 5-Alkylfuran-2(5H)-ones
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5-Alkylfuran-2(5H)-ones can be efficiently obtained using a one-pot approach, starting from methyl 3-nitropropanoate and aldehydes, in ethyl acetate, with Amberlyst A-21 as catalyst, in 60-90% overall yield. Copyright Taylor & Francis Group, LLC.
- Ma, Jie,Wang, Si Hong,Guan, Rong Tian
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p. 1229 - 1233
(2007/10/03)
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- Stepwise cross-couplings of a dibromo-γ-methylenebutenolide as an access to Z-configured α-alkenyl-γ-alkylidenebutenolides. Straightforward synthesis of the antibiotic lissoclinolide
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The Z-isomer of α-bromo-γ-(bromomethylene)butenolide was prepared from α-angelica lactone or levulinic acid in three and four steps, respectively. Successive Stille-couplings with an unsaturated stannane, with the potential to use a different second unsaturated stannane, involved the a?-substituent first and the a?-substituent thereafter. Thereby, α-alkenyl-γ-alkylidenebutenolides and their arene analogs were obtained Z-selectively.
- Sorg, Achim,Blank, Frederik,Bruckner, Reinhard
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p. 1286 - 1290
(2007/10/03)
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- Microwave assisted Suzuki reactions for the preparation of the antifungal 3-aryl-5-methyl-2,5-dihydrofuran-2-ones
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The Suzuki cross-coupling reaction of arylboronic acids with a bromo-furanone has been developed to prepare a series of substituted 2,5-dihydrofuran-2-ones related to the fungal metabolite, incrustoporin. A protocol of microwave heating was introduced to improve synthesis throughput. Georg Thieme Verlag Stuttgart.
- Mathews, Christopher J.,Taylor, John,Tyte, Melloney J.,Worthington, Paul A.
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p. 538 - 540
(2007/10/03)
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- A facile solid-phase synthesis of substituted 2(5H)-furanones with sulfone traceless linker
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A novel solid-phase synthetic method for substituted 2(5H)-furanones with traceless sulfone linker strategy has been developed. The products were obtained in good yields and excellent purities.
- Sheng, Shou-Ri,Huang, Pei-Gang,Zhou, Wei,Luo, Hai-Rong,Lin, Shu-Ying,Liu, Xiao-Ling
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p. 2603 - 2605
(2007/10/03)
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- Interconversion and decomposition of furanones
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The interconversion and decomposition of furan-2(3H)- and -2(5H)-one and their methylated derivatives were studied by following the changes in their photoelectron spectra during pyrolysis. Interconversion occurred at 300-400°C and decomposition at around 600°C giving CO and acrolein as the only products for the unsubstituted furanones. The experimental results suggest that decarbonylation takes place through the 2(3H) form as the common precursor.
- Xu, Zhi Ping,Mok, Chup Yew,Chin, Wee Shong,Huang, Hsing Hua,Li, Sheng,Huang, Wei
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p. 725 - 729
(2007/10/03)
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- IODINE (III) MEDIATED ACETOXY-LACTONIZATION OF UNSATURATED NITRILES
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4-Pentenenitriles reacted with PhI(OAc)2 in acetic acid, in the presence of 48percent HBF4, at 70 deg C, to afford the dihydro-5-acetoxymethyl-2(3H)-furanones in good yields.Similarly, 3-butenenitriles gave the dihydro-4-acetoxy-2(3H)-furanones, although in lower yields.Parallel experiments showed that, under the same conditions, 4-pentenoic and 3-pentenoic acids reacted much more easily and gave the same acetoxy-lactonization process at room temperature.
- Tiecco, Marcello,Testaferri, Lorenzo,Tingoli, Marco,Bartoli, Donatella
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p. 7139 - 7150
(2007/10/02)
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- A NEW METHOD FOR THE PREPARATION OF 3,5-DISUBSTITUTED BUTENOLIDES
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A convenient method for the transformation of suitably protected propargyl alcohols into 3,5-disubstituted butenolides has been developed.This organozirconium-based method transforms optically active propargyl alcohols into corresponding butenolides with no loss of optical activity.
- Buchwald, Stephen L.,Fang, Qun,King, Susan M.
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p. 3445 - 3448
(2007/10/02)
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- CHIRAL BUTENOLIDES IN DIELS-ALDER CYCLOADDITIONS WITH ISOPRENE AND CYCLOPENTADIENE
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Chiral α, β-butenolides react with isoprene at 125-220 deg C giving a 1:1 mixture of Diels-Alder regioisomers, selectivity being dramatically increased by the use of AlCl3 as catalyst.While these butenolides give no reaction with furan even in the presenceof catalysts, they react smoothly with cyclopentadiene, endo/exo selectivity being temperature dependent.
- Ortuno, Rosa M.,Batllori, Rosa,Ballesteros, Montserrat,Monsalvatje, Montserrat,Corbera, Jordi,et al.
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p. 3405 - 3408
(2007/10/02)
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- Michael Reaction of Conjugated Nitro Olefins with Carboxylic Acid Dianions and with Ester Enolates: New Synthesis of γ-Keto Acids and γ-Keto Esters
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Base-sensitive conjugated nitro olefins 2 reacted with lithium dianions of carboxylic acids 3 or with lithium enolates of esters 4 at a low temperature of ca. -100 deg C, and subsequent treatment of the Michael adducts with aqueous acid yielded γ-keto acids 5 or esters 5' in a one-pot operation, respectively.Results of both the reactions have been compared.Some applications of the resulting γ-keto esters in organic synthesis have also been demonstrated in lactone synthesis and cyclenone annulation.
- Miyashita, Masaaki,Yamaguchi, Ryuji,Yoshikoshi, Akira
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p. 2857 - 2863
(2007/10/02)
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