88158-68-3Relevant articles and documents
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.
Enantioselective Addition of Alkynyl Esters and Ethers to Aldehydes Catalyzed by a Cyclopropyl Amino Alcohol Based Zinc Catalyst
Bian, Qinghua,Li, Fengqi,Li, Shuoning,Ma, Sijie,Walsh, Patrick J.,Wang, Lifeng,Wang, Min,Zhong, Jiangchun,Zhou, Yun
supporting information, p. 60 - 64 (2019/12/30)
A novel and highly enantioselective synthesis of hydroxyalkynyl esters and ethers through the asymmetric addition of alkynyl esters or ethers to aldehydes promoted by a cyclopropyl amino alcohol based zinc catalyst has been developed. The method afforded a library of new enantioenriched hydroxyalkynol esters and ethers (up to 93percent yield; 95percent ee), and it was compatible with a broad range of functional groups. Moreover, it could be used in the synthesis of carbon-chain-elongated enantioenriched hydroxyalkynol esters and (2 R,5 R)-musclide-A1, a cardiotonic potentiating principle from musk.
Synthesis of Two Stereoisomers of Potentially Bioactive 13,19,20-Trihydroxy Derivative of Docosahexaenoic Acid
Ogawa, Narihito,Sone, Shinsaku,Hong, Song,Lu, Yan,Kobayashi, Yuichi
supporting information, p. 1735 - 1739 (2020/09/02)
The C16-C22 fragment with the acetylene terminus was constructed through the asymmetric dihydroxylation of the corresponding olefin, while the 15-iodo-olefin corresponding to the C11-C15 part was prepared via the asymmetric transfer hydrogenation of the corresponding acetylene ketone followed by hydrozirconation/iodination. Both pieces were joined by a Sonogashira coupling, and the product was further converted into the title compound via a Wittig reaction with the remaining C1-C10 segment and Boland reduction using Zn with TMSCl.
Asymmetric Kulinkovich Hydroxycyclopropanation of Alkenes Mediated by Titanium(IV) TADDOLate Complexes
Iskryk, Marharyta,Barysevich, Maryia,O?eka, Maksim,Adamson, Jasper,Kananovich, Dzmitry
supporting information, p. 1935 - 1948 (2019/04/26)
Asymmetric Kulinkovich cyclopropanation of carboxylic esters with prochiral alkenes is reported. The process is mediated by titanium(IV) (4 R,5 R)-TADDOLate complexes and affords correspondingly (Z)- or (E)-cyclopropanols with up to 84-87% ee in the event of intra- or intermolecular olefin ligand exchange in intermediate titanacyclopropane [titanium(II)-alkene] species. Configuration of the olefin double bond is preserved in the cyclopropane products, pointing out on total retention of configuration at Ti-C bond in the cyclopropane forming step. The results have been interpreted in the framework of ate complex mechanism, suggesting formation of pentacoordinated titanium ate species as a prerequisite of high enantiocontrol.
Copper-catalyzed aerobic oxidative coupling of terminal alkynes with α-carbonyl aldehydes: An expedient approach toward ynediones
Zhou, Bochao,Guo, Shiyu,Fang, Zheng,Yang, Zhao,Guo, Kai
supporting information, (2019/07/12)
An efficient and mild one-pot approach for copper-catalyzed aerobic oxidative coupling of α-carbonyl aldehydes with terminal alkynes toward ynediones has been developed. Moreover, a variety of ynediones were constructed under the optimized reaction condit
Concise Seven-Membered Oxepene/Oxepane Synthesis - Structural Motifs in Natural and Synthetic Products
Osei Akoto, Clement,Rainier, Jon D.
supporting information, p. 3529 - 3535 (2019/09/07)
This work outlines a suitable method for the synthesis of oxepane skeleton using iterative C-glycoside technology on the oxepene intermediate, which was synthesized utilizing Wilkinson's catalyst [Rh(PPh 3) 3 Cl] to generate the isom
Catalytic Generation and Chemoselective Transfer of Nucleophilic Hydrides from Dihydrogen
Pape, Felix,Brechmann, Lea T.,Teichert, Johannes F.
supporting information, p. 985 - 988 (2019/01/04)
Copper(I)–N-heterocyclic-carbene (NHC) complexes enabled the catalytic generation of nucleophilic hydrides from dihydrogen (H2) and their subsequent transfer to allylic chlorides. The highly chemoselective catalyst displayed no concomitant hydrogenation reactivity; in fact, the terminal double bond formed in the hydride transfer remained intact. Switching to deuterium gas (D2) allowed for regioselective monodeuteration with excellent isotope incorporation.
INTRAESOPHAGEAL ADMINISTRATION OF TARGETED NITROXIDE AGENTS FOR PROTECTION AGAINST IONIZING IRRADIATION-INDUCED ESOPHAGITIS
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Paragraph 0076; 0078, (2019/07/23)
Provided herein are compositions and related methods useful for prevention or mitigation of ionizing radiation-induced esophagitis. The compositions comprise compounds comprising a nitroxide-containing group attached to a mitochondria-targeting group. The
Quinocidin, acytotoxic antibiotic with anunusual 3,4-dihydroquinolizinium ring and michael acceptor reactivity toward thiols
Nakagawa, Yu,Sawaki, Yuki,Kimura, Takahiro,Tomura, Tomohiko,Igarashi, Yasuhiro,Ojika, Makoto
supporting information, p. 17894 - 17897 (2019/03/07)
Cytotoxicity-guided fractionation of the culture broth of Actinomadura sp. TP-A0019 led to the isolation of quinocidin (1), acytotoxic antibiotic with an unusual 3,4-dihydroquinolizinium ring. The structural assignment was made on the basis of high-field NMR experiments and chemical synthesis. Comparison ofthe spectral properties of 1 with those of its synthetic counterparts revealed that 1 is aracemic mixture of two enantiomers, which showed similar cytotoxicity against HeLa-S3 cells. Nucleophile-trap-ping experiments demonstrated that 1 captured 2-mer-captoethanol and N-acetyl-l-cysteine by means of aMi-chael addition-type reaction, but was inert toward 2-ami-noethanol and glycolic acid. Notably, the addition of 1 to thiols proceeded smoothly in neutral aqueous media at room temperature. In view of the thiol-trapping ability and the unusual structure, 1 provides aunique scaffold for designing drug leads and protein-labeling probes.
