370-07-0Relevant articles and documents
tert-Butylsulfinyl-fluoroacetate: Versatile reagent for the preparation of fluoroethylidenoate derivatives
Chevrie, David,Lequeux, Thierry,Pommelet, Jean-Claude
, p. 4759 - 4767 (2002)
The preparation of (Z)-α-fluoroalkenoates from readily available methyl-tert-butylsulfanyl- or tert-butylsulfinylfluoroacetate 1 or 5 is described. This short synthesis, based on a direct extrusion of SO2 from β-hydroxysulfoxides, presents a mo
Synthesis of α-Fluorinated Acrylates by a Palladium-Catalyzed Decarboxylative Olefination Reaction
Bouazzaoui, Ouafa,Rousée, Kevin,Mulengi, Joseph Kajima,Pannecoucke, Xavier,Bouillon, Jean-Philippe,Couve-Bonnaire, Samuel
, p. 3705 - 3715 (2018)
Ligand-free palladium-catalyzed subsequent decarboxylation/olefination reaction between 2-fluorinated acrylates and benzoic acids is reported. Valuable trisubstituted 2-fluoroacrylates and 2-trifluoromethylacrylates were produced in low to excellent yield
Thia-Wittig-like reactions as a new route for the stereoselective synthesis of (Z)-fluoroalkenoates
Chevrie, David,Lequeux, Thierry,Pommelet, Jean-Claude
, p. 1539 - 1541 (1999)
(matrix presented). Stereoselective syntheses of (Z)-fluoroalkenoates 3a-g have been developed in three steps from the readily available fluorosulfide 5 and aldehydes. This preparation, involving a Durst reaction, was highly stereoselective and led to flu
Organocatalyzed Sulfa-Michael Addition of Thiophenols on Trisubstituted α-Fluoroacrylates, a Straightforward Access to Chiral Fluorinated Compounds
Huang, Xin,David, Emilie,Jubault, Philippe,Besset, Tatiana,Couve-Bonnaire, Samuel
, p. 14055 - 14067 (2020/11/20)
In this manuscript, a simple and efficient sulfa-Michael addition reaction of aryl thiols to trisubstituted α-fluoro-α,β-unsaturated esters both in racemic and, for the first time, in enantioselective version is reported. The commercially available dimer of cinchona derivatives (DHQ)2PYR was used as a catalyst. This strategy showed a great tolerance for various substrates and substituents, providing fair to excellent yields, moderate to excellent diastereoselectivities (2:1 to >99:1), and low to good enantioselectivities (2 to 87%). The reaction has been applied to the synthesis of fluorinated analogues of diltiazem and tiazesim, both therapeutic agents.
Stereospecific synthesis of tri- and tetrasubstituted α-fluoroacrylates by mizoroki-heck reaction
Rousée, Kevin,Bouillon, Jean-Philippe,Couve-Bonnaire, Samuel,Pannecoucke, Xavier
supporting information, p. 540 - 543 (2016/02/18)
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.
PRODUCTION METHOD FOR ALPHA-FLUORO ACRYLIC ACID ESTERS
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Paragraph 0145; 0146, (2016/11/17)
An object of the present invention is to provide a process for producing α-fluoroacrylic acid esters at a high starting material conversion and a high yield. The present invention provides, as a means to achieve the object, a process for producing a compound represented by formula (1): wherein R2 and R2 are the same or different and each represent alkyl, fluoroalkyl, aryl optionally substituted with at least one substituent, halogen, or hydrogen; and R3 represents alkyl, fluoroalkyl, or aryl optionally substituted with at least one substituent, the process comprising step A ofreacting a compound represented by formula (2): wherein the symbols are as defined above, with carbon monoxide and an alcohol represented by formula (3): [in-line-formulae]R3—OH ??(3)[/in-line-formulae]wherein the symbol is as defined above, in the presence of a transition metal complex catalyst containing at least one bidentate phosphine ligand and a base to thereby obtain the compound represented by formula (1).
A substrate-driven approach to determine reactivities of α,β-unsaturated carboxylic esters towards asymmetric bioreduction
Tasnádi, Gábor,Winkler, Christoph K.,Clay, Dorina,Sultana, Nargis,Fabian, Walter M. F.,Hall, Mélanie,Ditrich, Klaus,Faber, Kurt
supporting information; experimental part, p. 10362 - 10367 (2012/10/08)
The degree of C=C bond activation in the asymmetric bioreduction of α,β-unsaturated carboxylic esters by ene-reductases was studied, and general recommendations to render these "borderline-substrates" more reactive towards enzymatic reduction are proposed. The concept of "supported substrate activation" was developed. In general, an additional α-halogenated substituent proved to be beneficial for enzymatic activity, whereas β-alkyl or β-aryl substituents were detrimental for the reactivity of nonhalogenated substrates, and α-cyano groups showed little effect. The alcohol moiety of the ester functionality was found to have a strong influence on the reaction rate. Overall, activities were determined by both steric and electronic effects. Biotransformation: The asymmetric bioreduction of α,β-unsaturated carboxylic esters by ene-reductases could be tuned by varying the degree of C=C bond activation (see scheme). An additional α-halogenated substituent proved to be beneficial for enzymatic activity, whereas β-alkyl or β-aryl substituents were detrimental for the reactivity of nonhalogenated substrates. Copyright
Synthetic utilization of 2-chloro-1,1,1,2-tetrafluoroethane
Notsu, Keiji,Zushi, Yasuyuki,Ota, Shin,Kawasaki-Takasuka, Tomoko,Yamazaki, Takashi
, p. 9200 - 9208 (2011/09/19)
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).
Highly efficient and stereoselective Julia-Kocienski protocol for the synthesis of α-fluoro-α,β-unsaturated Esters and Weinreb amides employing 3,5-bis(trifluoromethyl)phenyl (BTFP) sulfones
Alonso, Diego A.,Fuensanta, Monica,Gomez-Bengoa, Enrique,Najera, Carmen
experimental part, p. 1823 - 1829 (2009/07/11)
: α-Fluoroacetates 3 and Weinreb amide 4, bearing a α-[3,5-bis(trifluoromethyl)phenyl]sulfonyl (BTFP-sulfonyl) group at the α-position, are employed in the highly stereoselective synthesis of α-fluoro-α,β-unsaturated alkenoates and Weinreb amides, respectively. Aromatic and aliphatic aldehydes are condensed under extremely mild and simple reaction conditions using potassium carbonate in dimethylformamide at room temperature under solid-liquid phase-transfer catalysis conditions in good yields and high Z-diastereoselectivities, specially in the case of the fluorinated Weinreb amides. A detailed computational mechanistic study suggests a final non-concerted elimination of sulfur dioxide and 3,5-bis(trifluoromethyl)phenoxide and explains the observed high stereoselectivities for the reaction on the basis of thermodynamic and kinetic considerations.
Toward (Z)-selective Horner-Wadsworth-Emmons reaction of aldehydes with 2-fluoro-2-diethylphosphonoacetic acid
Sano, Shigeki,Teranishi, Rie,Nagao, Yoshimitsu
, p. 9183 - 9186 (2007/10/03)
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.
