- RUTHENIUM COMPLEX AND PRODUCTION METHOD THEREOF, CATALYST, AND PRODUCTION METHOD OF OXYGEN-CONTAINING COMPOUND
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PROBLEM TO BE SOLVED: To provide a ruthenium complex that is particularly useful as a catalyst for oxidizing a substrate having a carbon-hydrogen bond. SOLUTION: The ruthenium complex represented by the general formula (i) or a cis conformer thereof is provided. In the general formula (i), R1 represents H, a phenyl group or a substituted phenyl group; R2 represents H, a phenyl group or an alkyl group; L1 represents halogen or water molecule; L2 represents triphenylphosphine, pyridine, imidazole or dimethylsulfoxide; X represents halogen; and n represents 1 or 2. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPO&INPIT
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Paragraph 0140-0144
(2021/01/29)
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- SELECTIVE INHIBITORS OF NLRP3 INFLAMMASOME
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The present disclosure relates to compounds of Formula (I): (I); and to their pharmaceutically acceptable salts, pharmaceutical compositions, methods of use, and methods for their preparation. The compounds disclosed herein are useful for inhibiting the maturation of cytokines of the IL-1 family by inhibiting inflammasomes and may be used in the treatment of disorders in which inflammasome activity is implicated, such as autoinflammatory and autoimmune diseases and cancers.
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Paragraph 0605
(2019/02/15)
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- Poly(Alkyl Glycidate Carbonate)s as Degradable Pressure-Sensitive Adhesives
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Insertion of CO2 into the polyacrylate backbone, forming poly(carbonate) analogues, provides an environmentally friendly and biocompatible alternative. The synthesis of five poly(carbonate) analogues of poly(methyl acrylate), poly(ethyl acrylate), and poly(butyl acrylate) is described. The polymers are prepared using the salen cobalt(III) complex catalyzed copolymerization of CO2 and a derivatized oxirane. All the carbonate analogues possess higher glass-transition temperatures (Tg=32 to ?5 °C) than alkyl acrylates (Tg=10 to ?50 °C), however, the carbonate analogues (Td≈230 °C) undergo thermal decomposition at lower temperatures than their acrylate counterparts (Td≈380 °C). The poly(alkyl carbonates) exhibit compositional-dependent adhesivity. The poly(carbonate) analogues degrade into glycerol, alcohol, and CO2 in a time- and pH-dependent manner with the rate of degradation accelerated at higher pH conditions, in contrast to poly(acrylate)s.
- Beharaj, Anjeza,Ekladious, Iriny,Grinstaff, Mark W.
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supporting information
p. 1407 - 1411
(2019/01/14)
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- Total Synthesis of Solandelactone i
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Since the marine natural products solandelactones A-I were isolated from the hydroid Solanderia secunda and investigated by Seo et al. in 1996, considerable synthetic efforts toward these marine oxylipins followed. However, the structure elucidation of solandelactone I remained incomplete, and no synthesis has been reported. On the basis of our retrosynthetic analysis, the key building blocks were combined in a Horner-Wadsworth-Emmons reaction to create two common intermediates for the stereodivergent synthesis of all four diastereomers 1-4 matching the proposed structure of solandelactone I. Comparison of the published analytical data of natural product solandelactone I and data obtained from the synthetic endeavor toward diastereomers 1-4 enabled the structure assignment of isomer 3; the proposed biosynthetic pathway for marine oxylipins also supports the result.
- Eichenauer, Nils C.,Tschersich, Roxanne,Pietruszka, J?rg
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p. 2782 - 2790
(2015/12/09)
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- Α coccidiosis production of acrylic acid ester
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PROBLEM TO BE SOLVED: To provide a production method with which α-acyloxy acrylate can be obtained at high yield using commodity chemicals as raw materials and which is thereby suitable to be used industrially as a method for producing the α-acyloxy acrylate. SOLUTION: The method for producing the α-acyloxy acrylate includes a process for obtaining the α-acyloxy acrylate, which has a specific structure, using glycidic esters that have a specific structure. COPYRIGHT: (C)2012,JPOandINPIT
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Paragraph 0048; 0049
(2016/12/16)
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- Facile synthesis of glycidates via oxidation of acrylates with aqueous solution of naocl in the presence of ammonium salts
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Various glycidates were obtained in high yields via green oxidation of acrylates with aqueous solution of NaOCl in the presence of ammonium salts. The appropriate choice of ammonium salts fitting to the polarity of the substrates and the reaction under slightly basic conditions were essential for efficient reactions.
- Ochiai, Bungo,Hirano, Taiki
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p. 487 - 493
(2014/03/21)
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- Potent inhibitors of a shikimate pathway enzyme from Mycobacterium tuberculosis: Combining mechanism- and modeling-based design
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Tuberculosis remains a serious global health threat, with the emergence of multidrug-resistant strains highlighting the urgent need for novel antituberculosis drugs. The enzyme 3-deoxy-D-arabino-heptulosonate 7-phosphate synthase (DAH7PS) catalyzes the first step of the shikimate pathway for the biosynthesis of aromatic compounds. This pathway has been shown to be essential in Mycobacterium tuberculosis, the pathogen responsible for tuberculosis. DAH7PS catalyzes a condensation reaction between P-enolpyruvate and erythrose 4-phosphate to give 3-deoxy-D-arabino-heptulosonate 7-phosphate. The enzyme reaction mechanism is proposed to include a tetrahedral intermediate, which is formed by attack of an active site water on the central carbon of P-enolpyruvate during the course of the reaction. Molecular modeling of this intermediate into the active site reported in this study shows a configurational preference consistent with water attack from the re face of P-enolpyruvate. Based on this model, we designed and synthesized an inhibitor of DAH7PS that mimics this reaction intermediate. Both enantiomers of this intermediate mimic were potent inhibitors of M. tuberculosis DAH7PS, with inhibitory constants in the nanomolar range. The crystal structure of the DAH7PS-inhibitor complex was solved to 2.35 A. Both the position of the inhibitor and the conformational changes of active site residues observed in this structure correspond closely to the predictions from the intermediate modeling. This structure also identifies a water molecule that is located in the appropriate position to attack the re face of P-enolpyruvate during the course of the reaction, allowing the catalytic mechanism for this enzyme to be clearly defined.
- Reichau, Sebastian,Jiao, Wanting,Walker, Scott R.,Hutton, Richard D.,Baker, Edward N.,Parker, Emily J.
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scheme or table
p. 16197 - 16207
(2012/03/26)
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- Efficient epoxidation of electron-deficient alkenes with hydrogen peroxide catalyzed by [γ-PW10O38V2(μ-OH) 2]3-
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A divanadium-substituted phosphotungstate, [γ-PW10O 38V2(μ-OH)2]3- (I), showed the highest catalytic activity for the H2O2-based epoxidation of allyl acetate among vanadium and tungsten complexes with a turnover number of 210. In the presence of I, various kinds of electron-deficient alkenes with acetate, ether, carbonyl, and chloro groups at the allylic positions could chemoselectively be oxidized to the corresponding epoxides in high yields with only an equimolar amount of H2O2 with respect to the substrates. Even acrylonitrile and methacrylonitrile could be epoxidized without formation of the corresponding amides. In addition, I could rapidly (min) catalyze epoxidation of various kinds of terminal, internal, and cyclic alkenes with H;bsubesubbsubesub& under the stoichiometric conditions. The mechanistic, spectroscopic, and kinetic studies showed that the I-catalyzed epoxidation consists of the following three steps: 1) The reaction of I with H;bsubesubbsubesub& leads to reversible formation of a hydroperoxo species [I;circbsubesubbsubesubbsubesubcirccircbsupesup& (II), 2) the successive dehydration of II forms an active oxygen species with a peroxo group [ 2:2-O2)]3- (III), and 3) III reacts with alkene to form the corresponding epoxide. The kinetic studies showed that the present epoxidation proceeds via III. Catalytic activities of divanadium-substituted polyoxotungstates for epoxidation with H 2O2 were dependent on the different kinds of the heteroatoms (i.e., Si or P) in the catalyst and I was more active than [γ-SiW10O38V2(μ-OH)2] 4-. On the basis of the kinetic, spectroscopic, and computational results, including those of [γ-SiW10O38V 2(μ-OH)2]4-, the acidity of the hydroperoxo species in II would play an important role in the dehydration reactivity (i.e., k3). The largest k3 value of I leads to a significant increase in the catalytic activity of I under the more concentrated conditions. Copyright
- Kamata, Keigo,Sugahara, Kosei,Yonehara, Kazuhiro,Ishimoto, Ryo,Mizuno, Noritaka
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scheme or table
p. 7549 - 7559
(2011/08/03)
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- Epoxidation of α,β-unsaturated esters by dimejhyldioxirane
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Kinetic data for the epoxidation of a series of α,β-unsaturated esters, 2-10, by dimethyldioxirane in dried acetone are reported. These epoxidations are less sensitive to steric effects and occur with lower k 2 values than those for simple alkenes. Relative reactivity could be modeled based on a spiro transition state mechanism. The density function calculations were in good agreement with the krel values except for those compounds with cis-β-substituents.
- Baumstark,Vasquez,Aly,Sansone
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scheme or table
p. 183 - 186
(2011/06/24)
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- A convenient chemo-enzymatic synthesis and 18F-labelling of both enantiomers of trans-1-toluenesulfonyloxymethyl-2-fluoromethyl-cyclopropane
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The present report is concerned with a stereoselective, reliable route to trans-1,2-disubstituted cyclopropanes and in particular to (S,S)-1- tosyloxymethyl-2-fluoromethyl-cyclopropane (1) and (R,R)-1-tosyloxymethyl-2- fluoromethyl-cyclopropane (ent-1) as conformationally restricted, terminally fluorinated C4-building blocks for medicinal chemistry. The enzymatic kinetic resolution based synthesis of 1 and ent-1 utilises inexpensive, commercially available starting materials. It is based on enantiomeric resolution of rac-cyclopropane carboxylic esters using esterase from Streptomyces diastatochromogenes. Both enantiomers of 1 were prepared selectively in high overall yield over nine steps, starting from ethyl acrylate. The successful radiosynthesis of [18F]-1 and [18F]-ent-1 is also reported.
- Riss, Patrick Johannes,Roesch, Frank
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experimental part
p. 4567 - 4574
(2009/03/12)
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- Synthesis of optically active N6-alkyl derivatives of (R)-3-(adenin-9-yl)-2-hydroxypropanoic acid and related compounds
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Reaction of ethyl (R)-oxiranecarboxylate (2a) with various nucleobases (adenine, 6-chloropurine, thymine, cytosine, N6-benzoyladenine, 4-methoxy-5-methylpyrimidin-2(1H)-one and 4-methoxypyrimidin-2(1H)-one) afforded ethyl 3-substituted-2-hydroxypropanoates 4-10. Enantioselectivity of this reaction is dependent on the type of the base: 6-chloropurine, N6-benzoyladenine, 4-methoxy-5-methylpyrimidin-2(1H)-one, thymine and cytosine gave optically pure R enantiomers. In other cases, partial or complete racemization occurred. Optically pure ethyl (R)-3-(6-chloropurin-9-yl)-2-hydroxypropanoate (5a) was hydrolyzed to give (R)-3-(6-chloropurin-9-yl)-2-hydroxypropanoic acid (11). Reactions of 11 with various primary or secondary amines led to N6-substituted (R)-3-(adenin-9-yl)-2-hydroxypropanoic acids 14-19. Enantiomeric purity was determined from 1H NMR spectra measured in the presence of (-)-(R)-1-(9-anthryl)-2,2,2-trifluoroethan-1-ol.
- Krecmerova, Marcela,Budesinsky, Milos,Masojidkova, Milena,Holy, Antonin
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p. 931 - 950
(2007/10/03)
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- Epoxidation of terminal or electron-deficient olefins with H2O2, catalysed by Mn-trimethyltriazacyclonane complexes in the presence of an oxalate buffer
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A catalytic amount of an oxalate/oxalic acid buffer strongly enhances the catalytic properties of Mn-tmtacn complexes for epoxidation reactions with H2O2. Especially terminal olefins are easily epoxidized. Yields for e.g. allyl acetate or 1-hexene reach up to 99 % and 65 % on olefin and peroxide basis respectively. The reaction is stereospecific; there are no products of solvolysis.
- De Vos, Dirk E.,Sels, Bert F.,Reynaers, Mattias,Subba Rao,Jacobs, Pierre A.
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p. 3221 - 3224
(2007/10/03)
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- An efficient route to α,β-epoxy ketones of high enantiomerical purity
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Acylepoxides were obtained in high enantiomeric purity (ee = 92-99%) by addition of organolithium or Grignard reagents to enantiomerically pure methyl or ethyl 2,3-epoxypropanoates at low temperature (-85°C).
- Pegorier,Petit,Mambu,Larcheveque
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p. 1403 - 1405
(2007/10/02)
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- Preparation d'α-hydroxyesters et d'α-hydroxyaldehydes enantiomeriquement purs. Application a la synthese enantiospecifique de la pheromone sexuelle de la cochenille Pseudococcus comstocki
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Enantiomerically pure glycidic esters may be obtained in good yields by nitrous deamination of (S) or (R) serine; 2-bromo-3-hydroxy propionic acid is obtained and cyclized with alcoholic potash to give potassium glycidate; by reacting this salt with a sulfate, a primary iodide or an active bromide in acetonitrile in the presence of 18-crown-6, various glycidic esters were prepared.The ethyl glycidate reacts with lithiocuprates (alkyl or vinyl) but also with magnesiocuprates to afford a totally regiospecific reaction with the exclusive formation of α-hydroxyesters.The reaction is also possible with acetylides but it is necessary to use aluminium acetylides.With organolithium compounds reaction with the ester function of methyl glycidate occurs, leading to the formation of α-epoxyketones.The reduction of α-hydroxyesters (as protected form) with DIBAL-H at -70 deg C affords the corresponding α-hydroxyaldehydes in nearly quantitative yields.These reactions were applied to the synthesis of (R)-(+)-2,6-dimethyl-1,5-heptadien-3-ol acetate, the sex pheromone of the Comstock Mealybug, Pseudococcus comstocki.
- Larcheveque, Marc,Petit, Yves
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p. 130 - 139
(2007/10/02)
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- A SIMPLE PREPARATION OF R OR S GLYCIDIC ESTERS; APPLICATION TO THE SYNTHESIS OF ENANTIOMERICALLY PURE α-HYDROXYESTERS
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The simple preparation of enantiomerically pure α-hydroxyesters by the regioselective reaction of lithio and magnesiocuprates with glycidic esters 3 or 3' readily available from serine is described.
- Larcheveque, Marc,Petit, Yves
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p. 1993 - 1996
(2007/10/02)
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- Photochemical Reactions of Bicyclooctadienons
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A series of spirooxirano-substituted bicyclooctadienons have been prepared by Diels-Alder addition of dimethyl acetylenedicarboxylate to 2,4-cyclohexadienones, and their photochemistry was investigated.Upon direct exitation, they were found to aromatize by elimination of 2-carbonyloxirane which was trapped by ethanol to give ethyl glycidate.The acetophenone-sensitized reaction of bicyclooctadienones gave tricyclic isomeres whose formation by regiospecific di-?-methane rearrangement is discussed.
- Becker, Hans-Dieter,Ruge, Bernd
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p. 2189 - 2195
(2007/10/02)
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