- Chemoselective formation of cyclo-aliphatic and cyclo-olefinic 1,3-diolsviapressure hydrogenation of potentially biobased platform molecules using Kn?lker-type catalysts
-
The hydrogenative conversions of the biobased platform molecules 4-hydroxycyclopent-2-enone and cyclopentane-1,3-dione to their corresponding 1,3-diols are established using a pre-activated Kn?lker-type iron catalyst. The catalyst exhibits a high selectivity for ketone reduction, and does not induce dehydration. Moreover, by using different substituents of the ligand, thecis-transratio of the products can be affected substantially. A decent compatibility of this catalytic system with various structurally related substrates is demonstrated.
- Alsters, Paul L.,Chou, Khi Chhay,De Wildeman, Stefaan M. A.,Faber, Teresa,Hadavi, Darya,Han, Peiliang,Quaedflieg, Peter J. L. M.,Schwalb Freire, Alfonso J.,Verzijl, Gerard K. M.,van Slagmaat, Christian A. M. R.
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supporting information
p. 10102 - 10112
(2021/08/03)
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- Bio-based synthesis of cyclopentane-1,3-diamine and its application in bifunctional monomers for poly-condensation
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A novel and green route for the synthesis of cyclopentane-1,3-diamine (CPDA) from hemicellulosic feedstock is established in this work. Through many explorations and optimizations, the single successful multi-step synthesis was found to comprise: (1) the Piancatelli rearrangement of furfuryl alcohol to 4-hydroxycyclopent-2-enone (4-HCP), (2) a highly improved isomerization of4-HCPinto cyclopentane-1,3-dione (CPDO) using the Ru Shvo catalyst, (3) conversion ofCPDOinto cyclopentane-1,3-dioxime (CPDX), and (4) a mild oxime hydrogenation ofCPDXover Rh/C to afford the desiredCPDA. In addition, diastereomerically purecis- andtrans-isomers ofCPDAwere reacted with (A) bio-based lactones, and (B) 5-(hydroxymethyl)furfural (HMF) to synthesize novel bifunctional diol monomers with internal amide and imine groups, respectively. Monomer5, derived using γ-valerolactone (GVL), was successfully applied in the synthesis of polyurethanes.
- Alsters, Paul L.,De Wildeman, Stefaan M. A.,Hadavi, Darya,Han, Peiliang,Mogensen, Siri,Monsegue, Luciano G.,Noordijk, Jurrie,Quaedflieg, Peter J. L. M.,Verzijl, Gerard K. M.,van Slagmaat, Christian A. M. R.
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p. 7100 - 7114
(2021/09/28)
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- Synthesis of agelastatin A and derivatives premised on a hidden symmetry element leading to analogs displaying anticancer activity
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Concise total syntheses of (±)-7-hydroxy debromo agelastatin A (AglA), (±)-AglA, and 11-nitro AglA are presented based on an identified pseudo-symmetry element. This synthetic strategy was developed based on a desire to improve solubility of this potent anticancer agent while also developing a synthetic strategy that would enable late-stage variation of the pyrrole moiety. A stability study of pyrrole-derived carbinolamines revealed critical substituent effects impacting the equilibrium between the cyclic carbinolamine and keto pyrrole forms. 7-Hydroxy AglA existed primarily in the ketopyrrole form however the des-bromo variant existed primarily in the cyclic carbinolamine form. Cytotoxicity assays revealed activity for a 13-nitro AglA derivative (~14–63 μM) for breast cancer cells (MDA-MB-231 and MCF7) and a glioblastoma cell line (U87) while for 7-hydroxy des-bromo AglA, measurable activity was only observed against the glioblastoma cell line.
- Bertonha, Ariane F.,Ho, Matthew,Ingros, Alec,Kim, Minwoo,Reisenauer, Keighley,Robinson, Joshua,Romo, Daniel,Svatek, Haleigh,Taube, Joseph,Xue, Haoran
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supporting information
(2021/08/04)
-
- Application of hierarchical pore molecular sieve in preparation process of cyclopentadiene and JP-10 aviation fuel
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The invention relates to an application of a hierarchical pore molecular sieve in a the preparation process of cyclopentadiene and JP-10 aviation fuel. The hierarchical pore molecular sieve is one or two or more of an H-ZSM-5 molecular sieve, an H-beta molecular sieve, an H-Y molecular sieve, an H-USY molecular sieve, a La-Y molecular sieve and an H-MOR molecular sieve with a hierarchical pore structure, a sulfonated SBA-15 molecular sieve, a sulfonated MCM-41 molecular sieve, a sulfonated Ti-SBA-15 molecular sieve, a sulfonated MCM-41 molecular sieve, a sulfonated Zr-MCM-41 molecular sieve and a sulfonated Zr-SBA-15 molecular sieve; and the hierarchical pore structure comprises micropores and mesopores. The catalyst and the raw materials used in the method are cheap and easy to obtain, the preparation process is simple, and the hierarchical pore molecular sieve has high activity and selectivity for rearrangement reaction of furfuryl alcohol, hydrogenation reaction of hydroxyl cyclopentenone and dehydration reaction. The invention provides a cheap and efficient synthesis method for synthesizing the JP-10 aviation fuel from a lignocellulose-based platform compound furfuryl alcohol.
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Paragraph 0023; 0070-0086
(2021/07/01)
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- Double-metal cyanide as an acid and hydrogenation catalyst for the highly selective ring-rearrangement of biomass-derived furfuryl alcohol to cyclopentenone compounds
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Herein, novel green synthetic routes to 4-hydroxy-2-cyclopentenone (HCP) and 2-cyclopentenone (CPE) from biomass-derived furfuryl alcohol via double-metal cyanide catalysis are proposed. For the synthesis of HCP, in comparison to conventional solid acids (i.e., Amberlyst-15), MOFs with coordinatively unsaturated metal ions as pure Lewis acid sites exhibit advantageous catalytic selectivity in the reaction under an N2 atmosphere in a bi-phasic water/n-hexane solvent system. FeZn and FeZn-P result in an HCP yield of 77.4% and 88.2%, respectively. For the CPE synthesis, the reaction conditions are the same as those for HCP, except a mono-phasic water solvent system and H2 atmosphere were employed. In addition to the acid-catalyzed rearrangement reaction, FeZn-DMC exhibits catalytic hydrogenation capability via heterolytic cleavage of the H-H bond over Zn-N frustrated Lewis pairs, and a CPE yield of 61.5% is obtained. The DFT simulation indicates that the acid sites and catalytic acid sites are ascribed to the tri-coordinatively unsaturated Zn2+ site (Zn(N)3) on the catalyst surface. Moreover, the DMC catalyst shows excellent stability and recycling performance. This work not only provides an efficient and green catalytic system for CPE and HCP preparation but also demonstrates the interesting bifunctional catalysis of both acid and hydrogenation catalysis over DMC.
- Deng, Qiang,Deng, Shuguang,Gao, Rui,Li, Xiang,Lu, Chenxi,Tong, Zhikun,Wang, Jun,Yu, Lian,Zeng, Zheling,Zou, Ji-Jun
-
supporting information
p. 2549 - 2557
(2020/05/28)
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- A gradient reduction strategy to produce defects-rich nano-twin Cu particles for targeting activation of carbon-carbon or carbon-oxygen in furfural conversion
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Complexity of chemical linkages (C-C/C-H/C-O, C=C/C=O, or C-O-H/C-O-C) in biomass-derived molecules makes the selective activation of targeted bonds much more challenging, expecting well-defined catalysts and definite catalytically-active sites. This work demonstrates an effective gradient reduction strategy to control the definite structure of catalytically-active sites, affording defects-rich nano-twin Cu particles. This strategy just involves the reduction (calcination under H2) of CuII-containing layered double hydroxides (LDHs) simply with controlling the reduction gradient (interval time) of CuII species in two chemical micro-environments (CuII-O-CuII and CuII-O-MII/III/IV (M ≠ Cu)) in the brucite-like layer of LDHs. The nano-twin Cu particles efficiently promote the target activation of C-O and C=C in the conversion of furfural to cyclopentanone (CPO). With ~100% furfural conversion, the defects-rich nano-twin Cu particles afford a CPO selectivity of 92%, 50% higher than regular spherical Cu particles. The multi-stepped defect sites, originating from the planar defects, play a decisive role in promoting the CPO selectivity by facilitating the hydro-deoxygenation to C-O of 4-hydroxycyclopentenone (HCP) and hydrogenation to C=C of HCP or cyclopentenone.
- An, Zhe,Guo, Shaowei,He, Jing,Ma, Xiaodan,Shu, Xin,Song, Hongyan,Xiang, Xu,Zhang, Jian,Zhu, Yanru
-
-
- Method for cyclization conversion of furfuryl alcohol to form cyclopentenone
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The invention discloses a method for cyclization conversion of furfuryl alcohol to form cyclopentenone. The method comprises the following steps: mixing furfuryl alcohol with a solvent mixture according to a mass ratio of 1:(20-60) g/ml, and adding Lewis solid acid as a catalyst to carry out a reaction in an inert gas or hydrogen environment, wherein the reaction temperature is 120-160 DEG C. Through adoption of the technical scheme, 4-hydroxy-2-cyclopentenone/2-cyclopentenone is obtained by adopting a rearranging hydrolysis/hydrogenolysis method, so that the process is simple, operation is convenient, reaction conditions are mild, and the catalyst is cheap and easily available and can be recycled for multiple times. The method is easy to industrialize, excessive dependence on petroleum isreduced by the raw materials, and the environmental problems of halogen pollution are reduced. When the conversion rate of furfuryl alcohol for synthesizing 4-hydroxy-2-cyclopentenone reaches 95.2%,the yield is up to 88.2%; and when the conversion rate of furfuryl alcohol for synthesizing 2-cyclopentenone is up to 96%, the yield is up to 52.3%.
- -
-
Paragraph 0020-0024
(2019/10/01)
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- Concise Syntheses of ?"12-Prostaglandin J Natural Products via Stereoretentive Metathesis
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δ12-Prostaglandin J family is recently discovered and has potent anticancer activity. Concise syntheses of four δ12-prostaglandin J natural products (7-8 steps in the longest linear sequences) are reported, enabled by convergent stereoretentive cross-metathesis. Exceptional control of alkene geometry was achieved through stereoretention.
- Li, Jiaming,Ahmed, Tonia S.,Xu, Chen,Stoltz, Brian M.,Grubbs, Robert H.
-
supporting information
p. 154 - 158
(2019/01/04)
-
- TOTAL SYNTHESIS OF PROSTAGLANDIN J NATURAL PRODUCTS BY STEREORETENTIVE METATHESIS
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This invention relates generally to the synthesis of Δ12-Prostaglandin J product using stereoretentive ruthenium olefin metathesis catalysts supported by dithiolate ligands. Δ12- Prostaglandin J products were generated with excellent selectivity (>99% Z) and in moderate to high/good yields (47% to 80% yield; 58% to 80% yield).
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-
Paragraph 075
(2019/12/04)
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- Making JP-10 Superfuel Affordable with a Lignocellulosic Platform Compound
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The synthesis of renewable jet fuel from lignocellulosic platform compounds has drawn a lot of attention in recent years. So far, most work has concentrated on the production of conventional jet fuels. JP-10 is an advanced jet fuel currently obtained from fossil energy. Due to its excellent properties, JP-10 has been widely used in military aircraft. However, the high price and low availability limit its application in civil aviation. Here, we report a new strategy for the synthesis of bio-JP-10 fuel from furfuryl alcohol that is produced on an industrial scale from agricultural and forestry residues. Under the optimized conditions, bio-JP-10 fuel was produced with high overall carbon yields (≈65 %). A preliminary economic analysis indicates that the price of bio-JP-10 fuel can be greatly decreased from ≈7091 US$/ton (by fossil route) to less than 5600 US$/ton using our new strategy. This work makes the practical application of bio-JP-10 fuel forseeable.
- Li, Guangyi,Hou, Baolin,Wang, Aiqin,Xin, Xuliang,Cong, Yu,Wang, Xiaodong,Li, Ning,Zhang, Tao
-
supporting information
p. 12154 - 12158
(2019/08/12)
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- Switchable selectivity in Pd-catalyzed [3 + 2] annulations of γ-oxy-2-cycloalkenones with 3-oxoglutarates: C-C/C-C vs C-C/O-C bond formation
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Two complementary [3 + 2] annulation protocols between 3-oxoglutarates and cyclic γ-oxy-2-cycloalkenones, simply differing on the reaction temperature, are disclosed. These domino transformations allow C-C/O-C or C-C/C-C [3 + 2] annulations at will, via an intermolecular Pd-catalyzed C-allylation/intramolecular O- or C-1,4-addition sequence, respectively. In particular, exploiting the reversibility of the O-1,4-addition step, in combination with the irreversible C-1,4-addition/decarboxylation path, the intramolecular conjugate addition step could be diverted from the kinetic (O-alkylation) to the thermodynamic path (C-alkylation) thanks to a simple temperature increase. Crucial for the success of this bis-nucleophile/bis-electrophile [3 + 2] annulation is its well-defined step chronology in combination with the total chemoselectivity of the former step. This [3 + 2] C-C/O-C bond forming annulation protocol could be also extended to 1,3,5-triketones as well as 1,3-bis-sulfonylpropan-2-one bis-nucleophiles.
- Liu, Yang,Oble, Julie,Poli, Giovanni
-
supporting information
p. 1107 - 1115
(2019/06/08)
-
- Pharmacophore-Directed Retrosynthesis Applied to Rameswaralide: Synthesis and Bioactivity of Sinularia Natural Product Tricyclic Cores
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A pharmacophore-directed retrosynthesis strategy applied to rameswaralide provided simplified precursors bearing the common 5,5,6 (red) and 5,5,7 (blue) skeleton present in several cembranoid and norcembranoids from Sinularia soft corals. Key steps include a Diels-Alder lactonization organocascade delivering the common 5,5,6 core and a subsequent ring expansion affording a 5,5,7 core serviceable for the synthesis of rameswaralide. Initial structure-activity relationships of intermediates en route to the natural product have revealed interesting differential and selective cytotoxicity.
- Truax, Nathanyal J.,Ayinde, Safiat,Van, Khoi,Liu, Jun O.,Romo, Daniel
-
supporting information
p. 7394 - 7399
(2019/10/08)
-
- Synthesis of 3′-halo-5′-norcarbocyclic nucleoside phosphonates as potent anti-HIV agents
-
The synthesis and the antiviral evaluation of 3’-halo (iodo and fluoro) 5’-norcarbocyclic nucleoside phosphonates is described. No antiviral activity was observed against Zika virus, Dengue virus 2, HSV-1, HSV-2 and Chikungunya virus. In contrast, some of the synthesized compounds are potent inhibitors of the replication of HIV-1, comparatively to (R)-PMPA, with no concomitant cytotoxicity.
- Hamon, Nadège,Kaci, Malika,Uttaro, Jean-Pierre,Périgaud, Christian,Mathé, Christophe
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p. 642 - 654
(2018/03/22)
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- Highly Reactive and Tracelessly Cleavable Cysteine-Specific Modification of Proteins via 4-Substituted Cyclopentenone
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A rapid and cysteine-specific modification of proteins using 4-substituted cyclopentenone via a Michael addition tandem elimination reaction was developed. Compared to the classical method, this reaction featured fast kinetics with a stable product. More importantly, this conjugation could be tracelessly removed by exchange with a Michael addition donor. The conjugation and regeneration process not only exhibited little change to the structures or conformations of the proteins but also exhibited little disturbance to their biological functions, such as their enzymatic activities.
- Yu, Jian,Yang, Xiaoyue,Sun, Yang,Yin, Zheng
-
supporting information
p. 11598 - 11602
(2018/09/10)
-
- Synthesis of Guanine α-Carboxy Nucleoside Phosphonate (G-α-CNP), a Direct Inhibitor of Multiple Viral DNA Polymerases
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The synthesis of guanine α-carboxy nucleoside phosphonate (G-α-CNP) is described. Two routes provide access to racemic G-α-CNP 9, one via base construction and the other utilizing Tsuji-Trost allylic substitution. The latter methodology was also applied to the enantiopure synthesis of both antipodes of G-α-CNP, each of which showing interesting antiviral DNA polymerase activity. Additionally, we report an improved multigram scale preparation of the cyclopentene building block 10, starting material for the preferred Tsuji-Trost route to 9.
- Maguire, Nuala M.,Ford, Alan,Balzarini, Jan,Maguire, Anita R.
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p. 10510 - 10517
(2018/09/06)
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- Palladium-Catalyzed [3 + 2]-C-C/N-C Bond-Forming Annulation
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The synthesis of bi- and tricyclic structures incorporating pyrrolidone rings is disclosed, starting from resonance-stabilized acetamides and cyclic α,β-unsaturated-γ-oxycarbonyl derivatives. This process involves an intermolecular Tsuji-Trost allylation/intramolecular nitrogen 1,4-addition sequence. Crucial for the success of this bis-nucleophile/bis-electrophile [3 + 2] annulation is its well-defined step chronology in combination with the total chemoselectivity of the former step. When the newly formed annulation product carries a properly located o-haloaryl moiety at the nitrogen substituent, a further intramolecular keto α-arylation can join the cascade, thereby forming two new cycles and three new bonds in the same synthetic operation.
- Liu, Yang,Mao, Zhongyi,Pradal, Alexandre,Huang, Pei-Qiang,Oble, Julie,Poli, Giovanni
-
supporting information
p. 4057 - 4061
(2018/07/15)
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- Combining engineering and chemistry for the selective continuous production of four different oxygenated compounds by photo-oxidation of cyclopentadiene using liquid and supercritical CO2 as solvents
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A range of products is reported from the photo-oxidation of cyclopentadiene from photochemically generated singlet oxygen (1O2) using carbon dioxide (CO2) as a solvent and 5,10,15,20-tetrakis-(pentafluorophenyl)porphyrin (TPFPP) as a CO2-soluble photosensitizer. The endo-peroxide intermediate, generated from the reaction with singlet oxygen, is transformed into one of several different products in good yield depending on the conditions applied and by adding different reactors and reagents downstream of the photo-reactor, allowing the reaction products to be switched in one streamlined process. The addition of a thermal reactor facilitated the rearrangement of the endoperoxide to form Z-4,5-epoxy-2-pentanal. Quenching with thiourea yielded the syn-diol, (1R,3S)-cyclopent-4-ene-1,3-diol. Treatment with acid or base afforded furfuryl alcohol and 4-hydroxy-2-cyclopentenone respectively. High productivities for all products were obtained when compared to traditional batch reactions.
- Wu, Lingqiao,Abada, Zahra,Lee, Darren S.,Poliakoff, Martyn,George, Michael W.
-
supporting information
p. 3107 - 3112
(2017/12/15)
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- Catalytic cascade conversion of furfural to 1,4-pentanediol in a single reactor
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The synthesis of bio-based linear diols is the subject of many research studies. However, one of the main obstacles in industrial development is the difficulty in controlling product selectivity. Here, we report the catalytic conversion of furfural to 1,4-pentanediol (PD) in the presence of Ru supported on an ordered mesoporous carbon (CMK-3) under pressure of H2 and CO2 in water. In contrast to previous catalytic pathways, this work is distinct in that it yields 1,4-PD as an exclusive product, instead of a mixture of 1,2- and 1,5-PD as usual. Under optimized conditions, 1,4-PD was obtained in 90% yield, and in a one-pot reaction, directly from furfural. We disclose that the conversion of furfural to 1,4-PD followed an unusual catalytic route. It implies a bifunctional catalytic pathway based on sequential catalytic hydrogenation reactions and an acid-catalyzed Piancatelli's rearrangement.
- Liu, Fei,Liu, Qiaoyun,Xu, Jinming,Li, Lei,Cui, Yi-Tao,Lang, Rui,Li, Lin,Su, Yang,Miao, Shu,Sun, Hui,Qiao, Botao,Wang, Aiqin,Jér?me, Francois,Zhang, Tao
-
p. 1770 - 1776
(2018/04/30)
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- Method for preparing JP-10 aircraft fuel from furfuryl alcohol
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The invention relates to a method for preparing JP-10 aircraft fuel from furfuryl alcohol. The method for preparing the JP-10 aircraft fuel from furfuryl alcohol comprises the following four reactions: reaction I, in the presence of base catalyst or in the absence of a catalyst, preparing hydroxyl cyclopentenone from a furfuryl alcohol solution through a rearrangement reaction; reaction II, performing a D-A reaction on the hydroxyl cyclopentenone and cyclopentadiene so as to generate a C10 oxygen-containing compound; reaction III, performing hydrodeoxygenation on the C10 oxygen-containing compound generated in the former step so as to obtainendo-tetrahydrodicyclotadiene; and reaction IV, isomerizing the endo-tetrahydrodicyclotadiene, thereby obtaining exo-tetrahydrodicyclopentadiene, wherein theexo-tetrahydrodicyclopentadiene can be directly used as the JP-10 aircraft fuel. The catalyst and the raw materials used in the method are cheap and easy to obtain and have relatively high activity and selectivity for rearrangement reactions of furfuryl alcohol, D-A reactions of hydroxyl cyclopentenone and hydrodeoxygenation. The invention provides a cheap and efficient synthesis method forsynthesizing JP-10 aircraft fuel from a lignocelluloses based platform compound, namely tfurfuryl alcohol.
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Paragraph 0063; 0065; 0066; 0068; 0073; 0074
(2018/06/16)
-
- Method for preparing JP-10 aviation fuel from furfuryl alcohol
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The invention relates to a method for preparing JP-10 aviation fuel from furfuryl alcohol. The method for preparing JP-10 aviation fuel by taking the furfuryl alcohol as a raw material is totally divided into six reactions as follows: a first reaction of carrying out a rearrangement reaction on a furfuryl alcohol solution in the presence of a base catalyst or under the condition that any catalystis not added to prepare hydroxy cyclopentenone; a second reaction of reacting the hydroxy cyclopentenone and hydrogen under catalysis of a hydrogenation catalyst so as to prepare 1,3-cyclopendiol; a third reaction of dehydrating the 1,3-cyclopendiol to prepare cyclopentadiene; a fourth reaction of carrying out a D-A reaction on the cyclopentadiene to produce dicyclopentadiene; a fifth reaction ofhydrogenating the dicyclopentadiene to produce endo-tetrahydrodicyclotadiene; and a sixth reaction of performing isomerization on the endo-tetrahydrodicyclotadiene to produce hanging type tetrahydrodicyclopentadiene, wherein the prepared hanging type tetrahydrodicyclopentadiene can directly serve as the JP-10 aviation fuel. The invention provides a cheap high-efficiency synthetic method for synthesizing the JP-10 aviation fuel from a lignocelluloses-based platform chemical compound, namely furfuryl alcohol.
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Paragraph 0084; 0086; 0087; 0089; 0094
(2018/06/16)
-
- Method for preparing 4-hydroxycyclopent-2-enone from furfuryl alcohol
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The invention relates to a method for preparing 4-hydroxycyclopent-2-enone from furfuryl alcohol. According to the method, furfuryl alcohol is used as a raw material and subjected to a rearrangement reaction in the presence of an alkaline catalyst or in the absence of any catalyst so as to prepare 4-hydroxycyclopent-2-enone. The catalyst and raw material used in the invention are cheap and easily available; the preparation method is simple in process; and high activity and selectivity are obtained in the rearrangement reaction of furfuryl alcohol. The method provided by the invention is high-efficiency synthetic method for preparing 4-hydroxycyclopent-2-enone from a lignocelluloses-based platform compound, i.e., furfuryl alcohol.
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-
Paragraph 0034-0037
(2017/07/21)
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- Method for preparing 1,3-cyclopentanediol from furfuryl alcohol
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The invention relates to a method for preparing 1,3-cyclopentanediol from furfuryl alcohol. According to the method, furfuryl alcohol is used as a raw material, and 1,3-cyclopentanediol is prepared through two steps of reactions. The method comprises a first step of subjecting a furfuryl alcohol solution to a rearrangement reaction in the presence of an alkaline catalyst or in the absence of any catalyst so as to prepare hydroxycyclopentenone and a second step of reacting hydroxycyclopentenone with hydrogen under the catalysis of a hydrogenation catalyst so as to prepare 1,3-cyclopentanediol. The catalysts and raw materials used in the invention are cheap and easily available; the preparation method is simple in process; and high activity and selectivity are obtained in the rearrangement reaction of furfuryl alcohol and the hydrogenation reaction of hydroxycyclopentenone. The method provided by the invention is high-efficiency synthetic method for preparing 1,3-cyclopentanediol from a lignocelluloses-based platform compound, i.e., furfuryl alcohol.
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-
Paragraph 0039-0042
(2017/07/19)
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- Method for preparation of cyclopentadiene or dicyclopentadiene by furfuryl alcohol
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The invention relates to a method for preparation of cyclopentadiene or dicyclopentadiene by furfuryl alcohol. The method for preparation of cyclopentadiene or dicyclopentadiene by furfuryl alcohol as a raw material comprises the three-step reaction: a first step, under a condition with an alkali catalyst or under a condition with no addition of a catalyst, carrying out a rearrangement reaction of a furfuryl alcohol solution to prepare hydroxy cyclopentenone; a second step, under catalysis of a hydrogenation catalyst, carrying out a reaction of hydroxy cyclopentenone with hydrogen gas to prepare 1,3-cyclopendiol; and a third step, dehydrating 1,3-cyclopendiol to prepare cyclopentadiene or dicyclopentadiene. The used catalyst and raw materials are inexpensive and easy to obtain, the preparation process is simple, and high activity and selectivity are achieved for rearrangement reaction of furfuryl alcohol, hydrogenation reaction of hydroxy cyclopentenone and dehydration reaction of 1,3-cyclopendiol. The invention provides the cheap and efficient synthesis method for synthesis of cyclopentadiene or dicyclopentadiene with the lignocellulose based platform compound furfuryl alcohol.
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Paragraph 0043; 0044; 0045; 0046; 0047; 0048; 0049-0063
(2017/07/20)
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- Method for preparing JP-10 aviation fuel from furfuryl alcohol
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The invention relates to a method for preparing JP-10 aviation fuel from furfuryl alcohol. The method for preparing the JP-10 aviation fuel by adopting the furfuryl alcohol as a raw material comprises the following five steps: step I, enabling a furfuryl alcohol solution to have a rearrangement reaction to prepare hydroxylcyclopentenone under the condition of an alkaline catalyst or no catalyst; step II, enabling the hydroxylcyclopentenone to react with hydrogen under the catalysis of a hydrogenation catalyst to prepare 1,3-cyclopentanediol; step III, preparing cyclopentadiene or dicyclopentadiene by dehydrating the 1,3-cyclopentanediol; step IV, enabling the cyclopentadiene and the dicyclopentadiene to have an isomerization reaction to generate hanging dicyclopentadiene; and step V, hydrogenating the hanging dicyclopentadiene to generate hanging tetrahydro-dicyclopentadiene, and then rectifying and purifying to obtain the JP-10 aviation fuel. Raw materials used in the method are cheap and easy to obtain, the preparation process is simple, and the activity and selectivity for the rearrangement reaction of the furfuryl alcohol, the hydrogenation reaction of the hydrocyclopentenone and the dehydration reaction is relatively high. The invention provides a synthetic method with low cost and high efficiency for synthesizing the cyclopentadiene or the dicyclopentadiene from lignocelluloses-based platform compound and furfuryl alcohol.
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Paragraph 0059; 0060; 0061; 0062; 0063; 0064-0078
(2017/07/21)
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- Total synthesis of the antibiotic 4-hydroxycyclopent-2-en-1-one acrylate derivative EA-2801
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The first total synthesis of (±)-EA-2801, a naturally occurring 4-hydroxycyclopent-2-en-1-one acrylate produced by the fungus Trichoderma atroviridae UB-LMA, was achieved The synthesis started from furfuryl alcohol, manufactured industrially from furfural, produced from waste biomass such as corncobs or sugar cane bagasse. (±)-EA-2801 was synthesized in 5 steps and 71% overall yield starting from 4-hydroxycyclopent-2-en-1-one. Enantio-pure (R)- and (S)-EA-2801 were obtained from racemic mixture by preparative chiral supercritical fluid chromatography (SFC).
- Le Goff, Géraldine,Adelin, Emilie,Arcile, Guillaume,Ouazzani, Jamal
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supporting information
p. 2337 - 2339
(2017/05/29)
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- 4-VINYL-2-CYCLOPENTEN-1-ONE DERIVATIVES, THE PRODUCTION THEREOF, AND THE USE OF SAME AS AN ANTIBIOTIC AGENT
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The invention relates to a compound of general formula (I) wherein: R1 is a hydrogen atom or a C1 to C4 alkyl radical; R2 is a C1 to C4 hydroxyl or alkoxyl radical; and R3 and R4 are independently a hydrogen atom or a C1 à C4 alkyl radical; and the enantiomers and mixtures of enantiomers thereof, especially in a racemic form.
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Paragraph 0038; 056; 0057; 0058; 0059; 0060; 0061
(2017/05/19)
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- Synthesis of 6-Substituted 2-Pyrones Starting from Renewable Resources: Total Synthesis of Sibirinone, (E)-6-(Pent-1-en-1-yl)-2H-pyran-2-one, and (E)-6-(Hept-1-en-1-yl)-2H-pyran-2-one
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An atom-economic reaction sequence to 6-substituted 2-pyrones was developed starting from furfuryl alcohol, a renewable resource made from bran or bagasse, and aldehydes, utilizing a thermal rearrangement of cyclopentadienone epoxides as key step. Derivatives bearing a hydroxyalkyl side chain could be enzymatically resolved, providing access to enantiomerically pure 2-pyrones, or converted to alkenyl-substituted 2-pyrones such as naturally occurring sibirinone, (E)-6-(pent-1-en-1-yl)-2H-pyran-2-one, and (E)-6-(hept-1-en-1-yl)-2H-pyran-2-one.
- Dobler, Daniel,Reiser, Oliver
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p. 10357 - 10365
(2016/11/17)
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- Industrially scalable and cost-effective synthesis of 1,3-cyclopentanediol with furfuryl alcohol from lignocellulose
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A new route for the selective synthesis of renewable 1,3-cyclopentanediol was developed by the aqueous phase rearrangement of furfuryl alcohol to 4-hydroxycyclopent-2-enone followed by hydrogenation. The presence of a small amount of base catalysts is beneficial for the aqueous phase rearrangement of furfuryl alcohol to 4-hydroxycyclopent-2-enone. Such a promotion effect of base catalysts can be rationalized by restraining the generation of levulinic acid which may catalyze the polymerization of furfuryl alcohol. In the hydrogenation of 4-hydroxycyclopent-2-enone to 1,3-cyclopentanediol, an evident solvent effect was noticed. Higher carbon yields of 1,3-cyclopentanediol were obtained when tetrahydrofuran was used as the solvent. In the large scale tests with high initial concentrations of feedstocks, a high overall carbon yield (72.0%) of 1,3-cyclopentanediol was achieved over cheap catalysts (MgAl-HT and RANEY Ni). As a potential application, 1,3-cyclopentanediol as obtained was successfully used as a monomer in the synthesis of polyurethane.
- Li, Guangyi,Li, Ning,Zheng, Mingyuan,Li, Shanshan,Wang, Aiqin,Cong, Yu,Wang, Xiaodong,Zhang, Tao
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supporting information
p. 3607 - 3613
(2016/07/06)
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- Traceless Stereoinduction for the Enantiopure Synthesis of Substituted-2-Cyclopentenones
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The pseudoenantiomeric 4-O-Boc- and 4-OPMP-cyclopent-2-enones, readily available from hydroxymethylenefurane on multigram scale, are demonstrated to be exceptional building blocks for the synthesis of enantiopure 4-alkyl-5-(1′-hydroxyalkyl) substituted 2-cyclopentenones and derivatives thereof. The 4-OR substituent acts as a traceless stereoinducing element, conferring not only 1,2- but also 1,4-stereocontrol with excellent selectivity. The methodology developed here was applied for the rapid synthesis of natural products and biologically active 2-cyclopentenones such as TEI-9826, guaianes, and pseudoguaianolides. (Figure Presented).
- Arisetti, Nanaji,Reiser, Oliver
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- An Enantioselective Approach to 4-O-Protected-2-cyclopentene-l,4-diol Derivatives via a Rhodium-Catalyzed Redox-Isomerization Reaction
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Kinetic resolution of a series of cyclopentene-1,4-diol derivatives has been successfully achieved with enantiomeric excess up to 99.4% and a kf/ks ratio of 55 by a rhodium-catalyzed redox-isomerization reaction in a noncoordinating solvent.
- Ren, Kai,Zhao, Mengmeng,Hu, Bei,Lu, Bin,Xie, Xiaomin,Ratovelomanana-Vidal, Virginie,Zhang, Zhaoguo
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p. 12572 - 12579
(2016/01/09)
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- OXAZOLIDINONE HYDROXAMIC ACID COMPOUNDS FOR THE TREATMENT OF BACTERIAL INFECTIONS
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This invention pertains generally to treating bacterial infections using organic compounds of Formula I. In certain aspects, the invention pertains to treating infections caused by Gram-negative bacteria. (I) wherein X, Y, R1, R2, R3, R4 and R5 and defined herein.
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Page/Page column 178; 179
(2015/05/19)
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- Chemoenzymatic routes to cyclopentenols: The role of protecting groups on stereo- and enantioselectivity
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Enantiopure (R)-4-triisopropylsilyloxycyclopent-2-en-1-one was obtained through short sequences including either the enzymatic resolution of racemic cis-4-triisopropylsilyloxycyclopent-2-en-1-ol or the enzymatic desymmetrization of cis-cyclopent-2-en-1,3-diol. Alternatively, the enantiopure (S)-4-triisopropylsilyloxycyclopent-2-en-1-one was very efficiently obtained from diacetate of cis-cyclopent-2-en-1,3-diol using enzymatic desymmetrization with CAL-B. In these sequences, TIPS proved to be the best protecting group.
- Specklin, Simon,Dikova, Anna,Blanc, Aurélien,Weibel, Jean-Marc,Pale, Patrick
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p. 6987 - 6991
(2015/02/02)
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- Synthesis of Enantiomerically Pure 4-Hydroxy-2-cyclopentenones
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Conversion of furfuryl alcohol to 4-hydroxy-2-cyclopentenone was studied in a microreactor channel of 0.5 mm diameter and 1.5 m length. Addition of 1 M N-methylpyrrolidinone as a cosolvent significantly reduces the polymeric material normally formed during the reaction in purely aqueous solution. The reaction follows pseudo-first-order kinetics at constant pressure (200 bar) with the values of ΔHa = 18 ± 2 kcal/mol and ΔSa = -38 ± 3 cal/mol/K. At 240 C, 200 bar pressure, and residence time of 1.5 min, the product is obtained with 98% conversion and is isolated as a stable O-phenylacetyl derivative in 80% yield. This racemic mixture was resolved into enantiomerically pure forms by kinetic resolution with penicillin G acylase (E.C.3.5.1.11) immobilized on epoxy-activated polymer in 90-92% theoretical yield and >99% ee.
- Kumaraguru, Thenkrishnan,Babita, Panuganti,Sheelu, Gurrala,Lavanya, Kuna,Fadnavis, Nitin W.
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p. 1526 - 1530
(2014/01/06)
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- Enantioselective synthesis of 4-heterosubstituted cyclopentenones
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Racemic 4-hydroxycyclopentenone, readily derived from furfuryl alcohol, can be transformed via its O-Boc derivative to 4-acyloxy, 4-aryloxy-, 4-amino-, or 4-thio-substituted cyclopentenones with high enantioselectivity by palladium-catalyzed kinetic resolution via nucleophilic allylic substitutions. Applying this methodology, a short formal synthesis of ent-noraristeromycin was readily accomplished.
- Ulbrich, Kathrin,Kreitmeier, Peter,Vilaivan, Tirayut,Reiser, Oliver
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p. 4202 - 4206
(2013/06/04)
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- Conversion of furfural into cyclopentanone over Ni-Cu bimetallic catalysts
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The conversion of furfural into cyclopentanone over Ni-Cu bimetallic catalysts was studied under hydrogen atmosphere. Furfuryl alcohol, 4-hydroxy-2-cyclopentenone and 2-cyclopentenone were verified as three key intermediates. Rearrangement of the furan ring was independent of hydrogenation, starting from furfuryl alcohol rather than furfural. The opening and closure of the furan ring were closely related to the attack of a H2O molecule on the 5-position of furfuryl alcohol. Prior hydrogenation of the aldehyde group accounted for the different reactivity of furfural and furfuryl alcohol. The high selectivity of cyclopentanone was ascribed to the presence of 2-cyclopentenone.
- Yang, Yanliang,Du, Zhongtian,Huang, Yizheng,Lu, Fang,Wang, Feng,Gao, Jin,Xu, Jie
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supporting information
p. 1932 - 1940
(2013/09/24)
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- Asymmetric total syntheses of (-)-penicipyrone and (-)-tenuipyrone via biomimetic cascade intermolecular michael addition/cycloketalization
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The first total syntheses of (-)-penicipyrone and (-)-tenuipyrone were accomplished enantioselectively in 12 steps with an 11% yield and 6 steps with a 28% yield from the known 4-((tert-butyldimethylsilyl)oxy)-cyclopent-2-enone, respectively, by developing a biomimetic bimolecular cascade cyclization featuring an intermolecular Michael addition/cyclo-(spiro-)ketalization sequence. The relative, absolute stereochemistry and carbon connectivity of penicipyrone was further confirmed by X-ray crystallographic analysis and comparison of optical rotations.
- Song, Liyan,Yao, Hongliang,Zhu, Liangyu,Tong, Rongbiao
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supporting information
p. 6 - 9
(2013/03/28)
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- An epoxyisoprostane is a major regulator of endothelial cell function
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The goal of these studies was to determine the effect of 5,6-epoxyisoprostane, EI, on human aortic endothelial cells (HAEC). EI can form as a phospholipase product of 1-palmitoyl-2-(5,6-epoxyisoprostane E2)-sn-glycero-3-phosphocholine, PEIPC, a proinflammatory molecule that accumulates in sites of inflammation where phospholipases are also increased. To determine the effect of EI on HAEC, we synthesized several stereoisomers of EI using a convergent approach from the individual optically pure building blocks, the epoxyaldehydes 5 and 6 and the bromoenones 14 and 16. The desired stereoisomer of EI can be prepared from these materials in only six operations, and thus, large amounts of the product can be obtained. The trans/trans isomers had the most potent activity, suggesting specificity in the interaction of EI with the cell surface. EI has potent anti-inflammatory effects in HAEC. EI strongly inhibits the production of MCP-1, a major monocyte chemotactic factor, and either decreases or minimally increases the levels of 10 proinflammatory molecules increased by PEIPC. EI also strongly down-regulates the inflammatory effects of IL-1β, a major inflammatory cytokine. Thus EI, a hydrolytic product of PEIPC, has potent anti-inflammatory function.
- Zhong, Wei,Springstead, James R.,Al-Mubarak, Ramea,Lee, Sangderk,Li, Rongsong,Emert, Benjamin,Berliner, Judith A.,Jung, Michael E.
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p. 8521 - 8532
(2013/12/04)
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- Synthesis of a highly functionalized core of verrillin
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An efficient stereoselective synthesis of furanoverrillin (5), a highly functionalized core of verrillin (1), is reported. The synthetic strategy is based on constructing bicyclic lactone 17 prior to the 10-membered ring macrocyclization. The effect of the C4 methyl group on the furan reactivity is also discussed.
- Saitman, Alec,Theodorakis, Emmanuel A.
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supporting information
p. 2410 - 2413
(2013/06/27)
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- PREPARATION OF LUBIPROSTONE
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Aspects of the present application relate to process for the preparation of lubiprostone.
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Paragraph 0107
(2013/07/25)
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- Regio-and stereoselective synthesis of pyrrolo or azepine-fused cyclopenta[ d ]isoxazolines from 2- p -tolylsulfinylcyclopent-2-en-1-one
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Reactions of enantiopure 2-p-tolylsulfinylcyclopent-2-en-1-one with cyclic nitrones afforded pyrrolo or azepine-fused cyclopenta[d]isoxazolidines in high yields under mild conditions. Comparison of these results with those obtained with cyclopent-2-en-1-one as the dipolarophile shows that the sulfinyl group increases the reactivity of the enonic system and efficiently controls the π-facial and endo/exo selectivities of the cycloadditions, which are also dependent on the easy cycloreversion of the resulting compounds. Results obtained in reactions with other dipoles (benzonitrile oxides and those resulting from allenoate and PPh3) are also reported. 2013 Copyright Taylor and Francis Group, LLC.
- Garcia Ruano, Jose L.,Soriano, Jose F.,Fraile, Alberto,Martin, M. Rosario,Nunez, Alberto
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- Evaluation of a flow-photochemistry platform for the synthesis of compact modules
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A custom-made meso-scale continuous flow-photochemistry platform was evaluated with the aim to enable the synthesis of synthetically relevant amounts (>5 g, with the option of 10-100 g) of novel compact modules, whose synthesis is based upon a photochemical transformation. The flow-photochemistry concept relies on the irradiation of thin-layers (20-90 μm) of reactant dissolved in a suitable solvent that is pumped through the single-pass photoreactor. The commercially available Ehrfeld Photoreactor XL system was equipped with standard UV lamps (emission maximum at 254 nm) which are cheap, durable and low in power consumption (8 W). The flow photochemistry system was evaluated using a known intramolecular [2+2] cycloaddition reaction investigating influence of flow rate (irradiation time), layer-thickness and reactant concentration. After a short initial optimisation phase, the system delivered in a first run 6 g of tricycle 4 which was further successfully up-scaled to 48 g, demonstrating the robustness and reliability of this flow photoreactor-platform.
- Nettekoven, Matthias,Püllmann, Bernd,Martin, Rainer E.,Wechsler, David
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experimental part
p. 1363 - 1366
(2012/04/10)
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- Formal synthesis of merrilactone a using a domino cyanide 1,4-addition-aldol cyclization
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A formal synthesis of merrilactone A has been completed using a domino 1,4-addition-aldol process as the key step. Both iodo- and cyano-1,4-addition- aldol cyclizations were productive in forming the highly hindered C1-C9 bond linking vic-quaternary and tertiary stereocenters. The latter method was used to complete a formal total synthesis of the natural product.
- Nazef, Naim,Davies, Robert D. M.,Greaney, Michael F.
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supporting information; experimental part
p. 3720 - 3723
(2012/08/28)
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- IMPROVED PROCESSES FOR PREPARING PURE (3AR,4S,6R,6AS)-6-AMINO-2,2-DIMETHYLTETRAHDRO-3AH-CYCLOPENTA[D] [1,3]-DIOXOL-4-OL AND ITS KEY STARTING MATERIAL
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Provided herein is an improved, commercially viable and industrially advantageous process for the preparation of a ticagrelor intermediate, (3aR,4S,6R,6aS)-6-amino-2,2- dimethyltetrahydro-3aH-cyclopenta[d][l,3]-dioxol-4-ol, which is useful for preparing ticagrelor or a pharmaceutically acceptable salt thereof in high yield and purity. The present invention further relates to an improved process for the preparation of (lS,4R)-cis-4-acetoxy- 2-cyclopenten-l-ol, which is a key starting material in the preparation of the ticagrelor intermediate.
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Page/Page column 24
(2012/05/31)
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- Resolution of racemic 4-hydroxy-2-cyclopentenone with immobilized penicillin G acylase
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Enantiomerically pure 4-oxo-2-cyclopentenyl derivatives were prepared by kinetic resolution with penicillin G acylase (EC 3.5.1.11) immobilized on an epoxy activated polymer. The enzyme selectively hydrolyzes the phenylacetyl ester of the (S)-enantiomer t
- Kumaraguru, Thenkrishnan,Fadnavis, Nitin W.
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scheme or table
p. 775 - 779
(2012/09/05)
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- Microwave- or microreactor-assisted conversion of furfuryl alcohols into 4-hydroxy-2-cyclopentenones
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The conversion of a variety of furfuryl alcohols, derived from renewable non edible resources such as bran, into 4-hydroxy-2-cyclopentenones was accomplished using microwave irradiation. In subcritical water (220° C, 15.5 bar) without the need for any catalyst the reaction proceeds approximately two orders of magnitude faster with up to twice the yield compared to methods previously reported that apply conventional heating techniques. For the parent furfuryl alcohol the process could be transferred to a microreactor, allowing the synthesis of 4-hydroxy-2-cyclopentenone in a continuous flow system on multigram scale. Georg Thieme Verlag Stuttgart · New York.
- Ulbrich, Kathrin,Kreitmeier, Peter,Reiser, Oliver
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experimental part
p. 2037 - 2040
(2010/10/02)
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- The thio-adduct facilitated, enzymatic kinetic resolution of 4-hydroxycyclopentenone and 4-hydroxycyclohexenone
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The addition of 3,4-dimethoxybenzyl thiol 8, as a benzyl thiol surrogate, to racemic 4-hydroxycyclopent-2-enone 2 and 4-hydroxycyclohex-2-enone 15 gave the corresponding cis-adducts (±)-3-(3,4-dimethoxybenzylthio)-4- hydroxycyclopentanone 4b and (±)-3-(3,4-dimethoxybenzylthio)-4- hydroxycyclohexanone 16 with good diastereocontrol. In both cases, subsequent treatment with vinyl acetate, in the presence of a lipase enabled enantiomer resolution. Thus, (+)-16 and the acetate of its enantiomer, (-)-(1R,2S)-2-(3,4- dimethoxybenzylthio)-4-oxocyclohexyl acetate, (-)-17 were isolated in 98% enantiomeric excess. Based on the 1,4-dioxygenation pattern, (-)-17 can be used to prepare both enantiomers of 4-(tert-butyldimethylsilyloxy)cyclohex-2-enone 19. Firstly, saponification, with a sub-stoichiometric amount of NaOMe, followed by a one-pot silyl ether formation-sulfide elimination sequence gave (+)-19. Then using the same starting material a 6-step sequence, featuring a diastereoselective NaBH4 reduction and a Cope-type sulfoxide elimination, gave (-)-19.
- O'Byrne, Aisling,Murray, Cian,Keegan, Dearbhla,Palacio, Carole,Evans, Paul,Morgan, Ben S.
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supporting information; experimental part
p. 539 - 545
(2010/05/11)
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- Progress toward the total synthesis of (±)-havellockate
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Havellockate (1) was isolated from the soft coral Sinularia granosa located on the Havellock island in the Indian Ocean. This highly compact and polyoxygenated marine diterpene bears a cis-fused hydrindane core that contains eight stereogenic centers as well as a spiro-lactone. To the best of our knowledge, no syntheses of 1 have been reported yet. Herein, we describe the synthesis of the all-carbon framework of havellockate (1) in 18 chemical operations. Our approach highlights the efficiency and utility of the hydroxy-directed Diels-Alder (HDDA) reaction to quickly access the cis-fused hydrindane core and securing the correct stereochemistry at C6 and C7. Moreover, six of the eight stereogenic centers have been installed in the correct stereochemistry.
- Beingessner, Rachel L.,Farand, Julie A.,Barriault, Louis
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body text
p. 6337 - 6346
(2010/12/19)
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- Synthesis of functionalized bicyclo[3.2.0]heptanes - A study of the [2+2] photocycloaddition reactions of 4-hydroxycyclopent-2-enone derivatives
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A selection of 4-hydraxycyclopent-2-enone derivatives were prepared in enantiomerically pure form, and their photochemical [2+2] cycloaddition reactions with a variety of alkenes were studied, with a view to providing diversely functionalized bicyclo[3.2.0]heptanes. Intermolecular reactions provided the target structures in reasonable yields as a mixture of exo and endo adducts, in proportions which varied very little as a. function of the steric bulk of the reactants or the reaction conditions, The system was suitably adapted for an intramolecular reaction, which provided a single, stereochemically pure product, the convenient precursor of a rigid, concave, trioxygenated skeleton.
- Le Liepvre, Matthieu,Ollivier, Jean,Aitken, David J.
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scheme or table
p. 5953 - 5962
(2010/03/03)
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- CYCLOPENTENE DIOL MONOACETATE DERIVATIVES
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A process for the preparation of organic compounds of formula (I), wherein R1is as described herein.
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Page/Page column 9-10; 12
(2008/12/05)
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