- 2-Diethoxyphosphoryl alcanoic acid dianions (lithium α-lithiocarboxylates) IV. A direct route to 2-fluoro-2-alkenoic acids by the Horner synthesis. Application in the field of pyrethroids
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2-Diethoxyphosphoryl-2-fluoroacetic acid was converted into the lithium α lithiocarboxylate dianion by treatment with n-butyllithium in hexane/tetrahydrofuran at -70 deg C.The Horner reaction between this new dianion and carbonyl compounds gave various 2-fluoro-2alkenoic acids.Application of the method to the cis,trans caronaldehyde ethyl esters led to the 2-fluoroethenyl pyrethroid derivatives (Z-cis, E-cis, Z-trans, E-trans).
- Coutrot, Ph.,Grison, C.,Sauvetre, R.
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Read Online
- Stereoconvergent Synthesis of Monofluoroalkenes via Photoinduced Dual Decarboxylative Cross-Coupling of α-Fluoroacrylic Acids with Redox-Active Esters
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Herein, a new strategy for the synthesis of monofluoroalkenes via employing α-fluoroacrylic acids and N-hydroxyphthalimide (NHPI) redox-active esters as coupling partners has been developed. This decarboxylative reaction enabled the formation of C(sp2)-C(sp3) bonds to provide a practical and efficient approach for the construction of a variety of monofluoroalkenes, which are key structural motifs in organic chemistry, under mild reaction conditions. The protocol exhibited excellent functional group compatibility and delivered monofluoroalkene products with excellent Z-stereoselectivity. This work also provides a platform for the modification of complex biologically active molecules containing carboxylic acids.
- Lu, Xiao-Yu,Gao, Ang,Ge, Meng-Yuan,Xia, Ze-Jie,Liu, Qi-Le,Tao, Ting-Hua,Sun, Xiao-Mei
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p. 4654 - 4669
(2022/04/07)
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- Fluorine-containing carboxylic acid compound and preparation method thereof
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The invention provides a fluorine-containing carboxylic acid compound and a preparation method and application thereof. The preparation method comprises the steps that a fluorine-containing olefin compound and CO2 react in a solvent in the presence of a c
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Paragraph 0038-0048; 0054-0057
(2020/09/09)
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- Copper-Catalyzed Carboxylation of C-F Bonds with CO2
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An effective Cu-catalyzed selective formal carboxylation of C-F bonds with an atmospheric pressure of CO2 is reported. A variety of gem-difluoroalkenes, gem-difluorodienes, and α-trifluoro-methyl alkenes show high reactivity and selectivity for
- Yan, Si-Shun,Wu, Dong-Shan,Ye, Jian-Heng,Gong, Li,Zeng, Xin,Ran, Chuan-Kun,Gui, Yong-Yuan,Li, Jing,Yu, Da-Gang
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p. 6987 - 6992
(2019/08/26)
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- Development of the First Two-Pore Domain Potassium Channel TWIK-Related K+ Channel 1-Selective Agonist Possessing in Vivo Antinociceptive Activity
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The TWIK-related K+ channel, TREK-1, has recently emerged as an attractive therapeutic target for the development of a novel class of analgesic drugs, suggesting that activation of TREK-1 could result in pain inhibition. Here, we report the synthesis of a series of substituted acrylic acids (1-54) based on our previous work with caffeate esters. The analogues were evaluated for their ability to modulate TREK-1 channel by electrophysiology and for their in vivo antinociceptive activity (acetic acid-induced writhing and hot plate assays), leading to the identification of a series of novel molecules able to activate TREK-1 and displaying potent antinociceptive activity in vivo. Furyl analogue 36 is the most promising of the series.
- Vivier, Delphine,Soussia, Ismail Ben,Rodrigues, Nuno,Lolignier, Stéphane,Devilliers, Ma?ly,Chatelain, Franck C.,Prival, Laetitia,Chapuy, Eric,Bourdier, Geoffrey,Bennis, Khalil,Lesage, Florian,Eschalier, Alain,Busserolles, Jér?me,Ducki, Sylvie
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p. 1076 - 1088
(2017/02/19)
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- Stereospecific synthesis of tri- and tetrasubstituted α-fluoroacrylates by mizoroki-heck reaction
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Ligand-free, efficient, palladium-catalyzed Mizoroki-Heck reaction between methyl α-fluoroacrylate and arene or hetarene iodides is reported for the first time. The reaction is stereospecific and provides fair to quantitative yields of fluoroalkenes. The Mizoroki-Heck reaction starting from more hindered and usually reluctant trisubstituted acrylate, to access tetrasubstituted fluoroalkenes, is also reported. Finally, the use of a three-step synthesis sequence, including Mizoroki-Heck reaction, allows the synthesis of fluorinated analogues of therapeutic agents with high yield.
- Rousée, Kevin,Bouillon, Jean-Philippe,Couve-Bonnaire, Samuel,Pannecoucke, Xavier
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supporting information
p. 540 - 543
(2016/02/18)
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- PAIN RELIEF COMPOUNDS
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The present invention relates to the use of compounds for the treatment or prevention of pain in mammals, in particularly in human beings, and also to a process for preparing these compounds.
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Paragraph 0491
(2015/02/19)
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- A facile and mild approach for stereoselective synthesis of α-fluoro-α,β-unsaturated esters from α-fluoro-β-keto esters via deacylation
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The highly stereoselective olefination reaction of α-fluoro-β-keto esters for the synthesis of α-fluoro-α,β-unsaturated esters has been developed. The olefination combines nucleophilic addition, intramolecular nucleophilic addition, and elimination in one step, as well as provides a facile synthetic approach to α-fluoro-α,β-unsaturated esters which are important units in many biologically active compounds and useful precursors in a variety of functional-group transformations.
- Qian, Jinlong,Yi, Wenbin,Lv, Meifang,Cai, Chun
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p. 127 - 132
(2015/02/02)
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- An efficient synthesis of (Z)-α-fluorochalcones via the palladium-catalyzed cross-coupling reaction of (Z)-α-fluorocinnamoyl chloride with boronic acids
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An efficient synthesis of α-fluorochalcones (1,3-diphenyl-2- fluoroprop-2-en-1-one) based on the Suzuki-Miyaura palladium-catalyzed cross-coupling reaction of arylboronic acids with α-fluorocinnamoyl chlorides in the presence of Cs2CO3/su
- Eddarir, Said,Kajjout, Mohammed,Rolando, Christian
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p. 1735 - 1738
(2013/03/14)
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- Synthetic utilization of 2-chloro-1,1,1,2-tetrafluoroethane
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β-Substituted α-fluoro-α,β-unsaturated carboxylic acids have been successfully synthesized, usually in a (Z)-stereospecific manner by way of a stepwise or a one-pot three-step procedure starting from 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124), one of the major byproducts of the industrial process for tetrafluoroethene formation from chlorofluoromethane (HCFC-22). Get some Z's! β-Substituted α-fluoro-α,β- unsaturated carboxylic acids have been successfully synthesized from 2-chloro-1,1,1,2-tetrafluoroethane, one of the major byproducts of tetrafluoroethene formation from chlorofluoromethane. The products are usually obtained with Z stereoselectivity, by either a stepwise or a one-pot three-step procedure (see scheme).
- Notsu, Keiji,Zushi, Yasuyuki,Ota, Shin,Kawasaki-Takasuka, Tomoko,Yamazaki, Takashi
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experimental part
p. 9200 - 9208
(2011/09/19)
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- Toward (Z)-selective Horner-Wadsworth-Emmons reaction of aldehydes with 2-fluoro-2-diethylphosphonoacetic acid
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The stereoselective Horner-Wadsworth-Emmons reaction of aldehydes with 2-fluoro-2-diethylphosphonoacetic acid utilizing i-PrMgBr afforded (Z)-α-fluoro-α,β-unsaturated carboxylic acids as the major products.
- Sano, Shigeki,Teranishi, Rie,Nagao, Yoshimitsu
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p. 9183 - 9186
(2007/10/03)
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- A novel reaction of β,β'-dihydroxy acids or esters with vanadium(V) trichloride oxide. New entry to the stereoselective synthesis of α-fluoro- α,β-unsaturated acids and esters
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β,β'-Dihydroxy carboxylic acids and esters, readily prepared from dibromofluoroacetate and aldehydes, underwent deoxygenation, followed by elimination of aldehyde by the action of vanadium(V) trichloride oxide at the reflux temperature of chlorobenzene fo
- Ishihara, Takashi,Shintani, Atsuhiro,Yamanaka, Hiroki
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p. 4865 - 4868
(2007/10/03)
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- Synthetic studies for novel structure of α-nitrogenously functionalized α-fluorocarboxylic acids. Part III. Some reactions of α-bromo-α-fluorocarboxylic acids and their ethyl esters with sodium azide
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Synthesis of a novel group of α-azido-α-fluorocarboxylic acid derivatives has been attempted by azidation of the corresponding α-bromo-α-fluorocarboxylic acids or ethyl esters.Although ethyl azidofluoroacetate was obtained, over-azidation occurred very readily in most cases to afford geminally diazidated compounds.Attemped conversion of ethyl azidofluoroacetate into azidofluoroacetic acid by alkaline hydrolysis or by treatment with trimethylsilyl bromide resulted mainly in the formation of defluorinated products.It was found that, although α-fluorocarboxylates are generally considered stable, defluorination occurs under nucleophilic conditions if an additional labilizing group is present on the same carbon atom as the fluorine.
- Takeuchi, Yoshio,Takagi, Kumiko,Yamaba, Tomokazu,Nabetani, Manabu,Koizumi, Toru
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p. 149 - 154
(2007/10/02)
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- Synthesis of fluorinated enynes via 1-bromo 1-fluoro alkenes
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A stereospecific synthesis of fluorinated enynes was performed through palladium catalysed condensation of 1-bromo 1-fluoro 2-arylethylenes, synthetised from 1-carboxyl 1-fluoro 2-arylethylene with monosubstitued alkynes.
- Eddarir, Said,Francesch, Charlette,Mestdagh, Helene,Rolando, Christian
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p. 4449 - 4452
(2007/10/02)
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- Reaction du methylure de dimethylsulfoxonium avec les ester α-fluoro α-ethyleniques
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The reaction of dimethylsulfoxonium methylide with α-fluoro α-ethylenic esters: R1-CH=CF-COOR' leads to the formation of β-keto-sulfoxonium ylides 3: R1CH=CF-CO=C-H-S+(O)(CH3)2.Reaction of ylides 3 with anhydrous HCl, at room temperature, provides β-keto γ,γ-fluoro-ethylenic sulfoxonium salts, whose decomposition, at high temperatures, leads to the formation of fluorinated chloromethyl-ketones: R1-CH=CF-CO-CH2Cl, which are not available by other methods.
- Elkik, Elias,Imbeaux-Oudotte, Michele
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p. 861 - 866
(2007/10/02)
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