62592-78-3Relevant academic research and scientific papers
First Total Syntheses of Novel Non-Enzymatic Polyunsaturated Fatty Acid Metabolites and Their Identification in Edible Oils
Pavlí?ková, Tereza,Bultel-Poncé, Valérie,Guy, Alexandre,Rocher, Amandine,Reversat, Guillaume,Vigor, Claire,Durand, Thierry,Galano, Jean-Marie,Jahn, Ullrich,Oger, Camille
supporting information, p. 10090 - 10098 (2020/07/24)
Oxidative stress (OS) is an in vivo process leading to free radical overproduction, which triggers polyunsaturated fatty acid (PUFA) peroxidation resulting in the formation of racemic non-enzymatic oxygenated metabolites. As potential biomarkers of OS, their in vivo quantification is of great interest. However, since a large number of isomeric metabolites is formed in parallel, their quantification remains difficult without primary standards. Three new PUFA-metabolites, namely 18-F3t-isoprostane (IsoP) from eicosapentaenoic acid (EPA), 20-F4t-neuroprostane (NeuroP) from docosahexaenoic acid (DHA) and 20-F3t-NeuroP from docosapentaenoic acid (DPAn-3) were synthesized by two complementary synthetic strategies. The first one relied on a racemic approach to 18(RS)-18-F3t-IsoP using an oxidative radical anion cyclization as a key step, whereas the second used an enzymatic deracemization of a bicyclo[3.3.0]octene intermediate obtained from cyclooctadiene to pursue an asymmetric synthesis. The synthesized metabolites were applied in targeted lipidomics to prove lipid peroxidation in edible oils of commercial nutraceuticals.
Drastic fluorine effect: Complete reversal of the selectivity in the Au-catalyzed hydroalkoxylation reaction of fluorinated haloalkynes
Cloutier, Mélissa,Mamone, Marius,Paquin, Jean-Fran?ois
supporting information, p. 5969 - 5972 (2020/06/04)
The gold-catalyzed hydration reaction of haloalkynes is highly regioselective producing 2-halomethylketones as the sole products. Herein, we document a drastic fluorine effect where the reaction of 1-halo-3,3-difluoroalkynes as substrates leads to a complete reversal of selectivity and produces 3,3-difluoroesters as the unique products.
Au-catalyzed intramolecular hydroalkoxylation of gem-difluorinated alkynols
Hamel, Jean-Denys,Paquin, Jean-Fran?ois
, p. 11 - 23 (2018/10/20)
The intramolecular hydroalkoxylation of gem-difluorinated alkynols was found possible under Au catalysis, allowing for the preparation of a series of fluorinated heterocycles. The nature of the solvent was found to be especially critical in the cyclizatio
Remote Cooperative Group Strategy Enables Ligands for Accelerative Asymmetric Gold Catalysis
Wang, Zhixun,Nicolini, Corrado,Hervieu, Cedric,Wong, Yuk-Fai,Zanoni, Giuseppe,Zhang, Liming
supporting information, p. 16064 - 16067 (2017/11/22)
An accelerative asymmetric gold catalysis is achieved for the first time via chiral ligand metal cooperation. An asymmetrically positioned remote amide group in the designed chiral binaphthyl-based ligand plays the essential role of a general base catalyst and selectively accelerates the cyclizations of 4-allen-1-ols into one prochiral allene face. The reactions are mostly highly enantioselective with achiral substrates, and due to the accelerated nature of the catalysis catalyst loadings as low as 100 ppm are allowed. With a pre-existing chiral center at any of the backbone sp3-carbons, the reaction remained highly efficient and most importantly maintained excellent allene facial selectivities regardless of the substrate stereochemistry. By using different combinations of ligand and substrate enantiomers, it is now possible to access all four stereoisomers of versatile 2-vinyltetrahydrofurans with exceedingly high selectivity. The underpinning design of this chemistry reveals a novel and conceptually distinctive strategy to tackle challenging asymmetric gold catalysis, which to date has relied on decelerative asymmetric steric hindrance approaches.
TETRASUBSTITUTED ALKENE COMPOUNDS AND THEIR USE
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Page/Page column 66, (2016/12/22)
Disclosed herein are compounds, or pharmaceutically acceptable salts thereof, and methods of using the compounds for treating breast cancer by administration to a subject in need thereof a therapeutically effective amount of the compounds or pharmaceutically acceptable salts thereof. The breast cancer may be an ER-positive breast cancer and/or the subject in need of treatment may express a mutant ER-α protein.
Total syntheses and in vivo quantitation of novel neurofuran and dihomo-isofuran derived from docosahexaenoic acid and adrenic acid
De La Torre, Aurlien,Lee, Yiu Yiu,Mazzoni, Attilio,Guy, Alexandre,Bultel-Ponc, Valrie,Durand, Thierry,Oger, Camille,Lee, Jetty Chung-Yung,Galano, Jean-Marie
supporting information, p. 2442 - 2446 (2015/01/30)
Neurofurans (NeuroFs) and dihomo-isofurans (dihomo-IsoFs) are produced in vivo by non-enzymatic free-radical pathways from docosahexaenoic and adrenic acids, respectively. As these metabolites are produced in minute amounts, their analyses in biological samples remain challenging. Syntheses of neurofuran and dihomo-isofurans described are based on a pivotal strategy, thanks to an enantiomerically enriched intermediate, which allowed, for the first time, access to both families: the alkenyl and enediol. Owing to this formation, quantitation of specific NeuroF and dihomo-IsoFs in biological samples was attainable.
A palladium/chiral amine co-catalyzed enantioselective dynamic cascade reaction: Synthesis of polysubstituted carbocycles with a quaternary carbon stereocenter
Ma, Guangning,Afewerki, Samson,Deiana, Luca,Palo-Nieto, Carlos,Liu, Leifeng,Sun, Junliang,Ibrahem, Ismail,Cordova, Armando
supporting information, p. 6050 - 6054 (2013/07/05)
Polysubstituted 5- and 6-membered carbocycles were synthesized by the title reaction. The one-pot dynamic relay process generates four new stereocenters, including a quaternary carbon center, in a highly enantioselective fashion (99.5:0.5→99:0.5 e.r.) by using a simple combination of palladium and chiral amine co-catalysts. Copyright
O -substituted alkyl aldehydes for rhodium-catalyzed intermolecular alkyne hydroacylation: The utility of methylthiomethyl ethers
Parsons, Scott R.,Hooper, Joel F.,Willis, Michael C.
supporting information; experimental part, p. 998 - 1000 (2011/05/15)
Combining α-methylthiomethyl (MTM) ether substituted aldehydes and 1-alkynes in the presence of [Rh(dppe)]ClO4 results in efficient intermolecular alkyne hydroacylation to deliver α-O-MTM-substituted enone products. The product MTM ethers can be converted to the free hydroxyl group either in situ, by the addition of water to the completed reaction, or in a separate operation, by the action of silver nitrate.(Figure Presented)
Preparation of highly hindered polyenes with tert-butyl groups in internal positions
Betz, Markus,Hopf, Henning,Ernst, Ludger,Jones, Peter G.,Okamoto, Yoshio
scheme or table, p. 231 - 247 (2011/03/19)
The conjugated tetraenes 3 and 4 a-c have been prepared and shown to possess an orthogonal structure. This was not only demonstrated by their spectroscopic properties and X-ray structural analysis of solid representatives (e.g., 4 a-c) but also by the res
Synthesis of [3-13C]-, [4-13C]- and [11- 13C]-porphobilinogen
Dawadi, Prativa B. S.,Schulten, Els A. M.,Lugtenburg, Johan
experimental part, p. 341 - 349 (2011/07/08)
[4-13C]-porphobilinogen 1a, [3-13C]-porphobilinogen 1b and [11-13C]-porphobilinogen 1c are prepared from [1- 13C]-3-(tetrahydropyran-20-yloxy)-propionaldehyde 2a, methyl [4- 13C]-4-nitrobutyrate 3b and [1-13C]-isocyanoacetonitrile 5c, respectively. The building blocks 2, 3 and 5 can be prepared efficiently in any isotopomeric form. Via base-catalyzed condensation of these building blocks porphobilinogen can be enriched with 13C and 15N stable isotopes at any position and combination of positions. Copyright
