88159-03-9Relevant 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.
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.
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.
Stereoselective Synthesis of Exocyclic Tetrasubstituted Vinyl Halides via Ru-Catalyzed Halotropic Cycloisomerization of 1,6-Haloenynes
Trost, Barry M.,Kalnmals, Christopher A.
supporting information, p. 2346 - 2349 (2017/05/12)
Herein, a ruthenium-catalyzed cycloisomerization that transforms 1,6-haloenynes into 5-membered carbo- and heterocycles that bear exocyclic, stereodefined, tetrasubstituted vinyl halides is reported. The reaction is insensitive to air and water, tolerates a variety of functional groups, and proceeds with good to excellent stereoselectivity and yield.
Carreira alkynylations with paraformaldehyde. A mild and convenient protocol for the hydroxymethylation of complex base-sensitive terminal acetylenes via alkynylzinc triflates
Hale, Karl J.,Xiong, Ziyue,Wang, Liping,Manaviazar, Soraya,Mackle, Ryan
supporting information, p. 198 - 201 (2015/01/30)
A new synthetic protocol for the hydroxymethylation of terminal acetylenes is described that involves stoichiometric Carreira alkynylation with solid paraformaldehyde (HO[CH2O]nH) in PhMe at 60 °C. Significantly, the method can be su
Highly Stereoselective Intermolecular Haloetherification and Haloesterification of Allyl Amides
Soltanzadeh, Bardia,Jaganathan, Arvind,Staples, Richard J.,Borhan, Babak
supporting information, p. 9517 - 9522 (2015/08/11)
An organocatalytic and highly regio-, diastereo-, and enantioselective intermolecular haloetherification and haloesterification reaction of allyl amides is reported. A variety of alkene substituents and substitution patterns are compatible with this chemistry. Notably, electronically unbiased alkene substrates exhibit exquisite regio- and diastereoselectivity for the title transformation. We also demonstrate that the same catalytic system can be used in both chlorination and bromination reactions of allyl amides with a variety of nucleophiles with little or no modification. A highly regioselective intermolecular haloetherification that proceeds with excellent enantioselectivity, catalyzed by cinchona alkaloid dimers, is reported. The regioselectivity is preserved for unbiased alkyl substituted allyl amides with either E or Z geometry. (DHQD)2PHAL=hydroquinidine 1,4-phthalazinediyl diether.
Studies culminating in the total synthesis and determination of the absolute configuration of (-)-saudin
Boeckman Jr., Robert K.,Rosario Ferreira, Maria Rico Del,Mitchell, Lorna H.,Shao, Pengcheng,Neeb, Michael J.,Fang, Yue
experimental part, p. 9787 - 9808 (2012/02/05)
A full account of studies that culminated in the total synthesis of both antipodes and the assignment of its absolute configuration of Saudin, a hypoglycemic natural product. Two approaches are described, the first proceeding though bicyclic lactone intermediates and related second monocyclic esters. The former was obtained via asymmetric Diels-Alder cycloaddition and the latter by an asymmetric annulation protocol. Both approaches employ a Lewis acid promoted Claisen rearrangement, with the successful approach taking advantage of bidentate chelation to control the facial selectivity of the key Claisen rearrangement.
Total synthesis of xanthanolides
Matsuo, Kazumasa,Ohtsuki, Keiko,Yoshikawa, Takashi,Shishido, Kozo,Yokotani-Tomita, Kaori,Shindo, Mitsuru
scheme or table, p. 8407 - 8419 (2010/12/19)
The total synthesis and determination of the absolute configuration of (+)- and (-)-sundiversifolide have been achieved via intramolecular acylation and Wittig-lactonization as the key steps. The xanthanolide sesquiterpene lactones, 8-epi-xanthatin (1), d
Design and synthesis of (135)-methyl-substituted arachidonic acid analogues: Templates for novel endocannabinoids
Papahatjis, Demetris P.,Nahmias, Victoria R.,Nikas, Spyros P.,Schimpgen, Marion,Makriyannis, Alexandras
supporting information; experimental part, p. 4091 - 4099 (2010/08/05)
Two novel methyl-substituted arachidonic acid derivatives were prepared in an enantioselective manner from commercially available chiral building blocks, and were found to be excellent templates for the development of (13S)methyl-substituted anandamide an
