- Electrochemical Synthesis of Fluorinated Ketones from Enol Acetates and Sodium Perfluoroalkyl Sulfinates
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The electrochemical synthesis of fluorinated ketones from enol acetates and RfSO2Na in an undivided cell under constant current conditions was developed. The electrosynthesis proceeded via perfluoroalkyl radical generation from sodium perfluoroalkyl sulfinate followed by addition to the enol acetate and transformation of the resulting C radical to a fluorinated ketone. The method is applicable to a wide range of enol acetates and results in the desired products in yields of 20 to 85%.
- Vil’, Vera A.,Merkulova, Valentina M.,Ilovaisky, Alexey I.,Paveliev, Stanislav A.,Nikishin, Gennady I.,Terent’ev, Alexander O.
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supporting information
p. 5107 - 5112
(2021/06/30)
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- Rational Design and Development of Low-Price, Scalable, Shelf-Stable and Broadly Applicable Electrophilic Sulfonium Ylide-Based Trifluoromethylating Reagents
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The development of two highly reactive electrophilic trifluoromethylating reagents (trifluoromethyl)(4-nitrophenyl)bis(carbomethoxy)methylide (1g) and (trifluoromethyl)(3-chlorophenyl)bis(carbomethoxy)methylide (1j) through structure-activity study was described. Under mild conditions, reagent 1g reacted with β-ketoesters and silyl enol ethers to give α-trifluoromethylated-β-ketoesters or α-trifluoromethylated ketones in high yields. In addition, reagent 1g could serve as a trifluoromethyl radical for a variety of trifluoromethylative transformations under visible light irradiation, including radical trifluoromethylation of electron-rich indoles and pyrroles and sodium aryl sulfinates as well as trifluoromethylative difunctionalization with styrene derivatives. On the other hand, as a complimentary, under reductive coupling conditions, reagent 1j reacted with a variety of (hetero)aryl iodides for the formation of trifluoromethylated (hetero)arenes.
- Ge, Hangming,Ling, Yijing,Liu, Yafei,Lu, Long,Shen, Qilong
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p. 1667 - 1682
(2021/05/28)
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- Scissoring Enaminone C=C Double Bond by Free Radical Process for the Synthesis of α-Trifluoromethyl Ketones with CF3SO2Na
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The C=C double bond cleavage on tertiary enaminones, enabling the formation of a new C-CF3 bond, has been realized as a practical method for the synthesis of α-trifluoromethyl ketones with only the promotion of TBHP and ambient heating. Control experiments support that the reactions proceed via a featured free radical process. The deuterium labeling experiment employing D2O indicates that water participated in the product formation by donating the hydrogen atom for the newly generated α-C-H bond in the product.
- Gan, Lu,Yu, Qing,Liu, Yunyun,Wan, Jie-Ping
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p. 1231 - 1237
(2020/12/21)
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- METHOD FOR PRODUCING α-FLUOROALKYL KETONE AND β-FLUOROALKYL ALCOHOL
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PROBLEM TO BE SOLVED: To provide a method for producing α-fluoroalkyl ketone and β-fluoroalkyl alcohol conveniently, inexpensively and efficiently. SOLUTION: A method for producing α-fluoroalkyl ketone represented by formula (II) (where Rf is a fluoroalkyl group) includes reacting an alkyne compound represented by formula (I) (where R1 is a chain hydrocarbon group, cyclic aliphatic hydrocarbon group, aromatic hydrocarbon group, heterocyclic group, -OR3, -NR4R4', R2 is a hydrogen atom, trialkylsilyl group, diallyl alkylsilyl group, or triallylsilyl group), in the presence of a radical initiator, with a fluoroalkyl sulfonic acid. SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
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Paragraph 0073-0075
(2020/07/03)
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- On the reactivity of anodically generated trifluoromethyl radicals toward aryl alkynes in organic/aqueous media
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An in-depth study of the reaction of electrochemically generated trifluoromethyl radicals with aryl alkynes in the presence of water is presented. The radicals are readily generated by anodic oxidation of sodium triflinate, an inexpensive and readily avai
- Jud, Wolfgang,Kappe, C. Oliver,Cantillo, David
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p. 3529 - 3537
(2019/04/14)
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- Regioselective Gold-Catalyzed Hydration of CF3- and SF5-alkynes
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The regioselective gold-catalyzed hydration of CF3- and SF5-alkynes is described. The corresponding trifluoromethylated and pentasulfanylated ketones are obtained in up to 91% yield as single regioisomers showcasing the use of CF3 and SF5 as highly efficient directing groups in this reaction. Notably, this transformation represents the first use of CF3- and SF5-alkynes in gold catalysis.
- Cloutier, Mélissa,Roudias, Majdouline,Paquin, Jean-Fran?ois
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p. 3866 - 3870
(2019/05/24)
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- Photocatalytic decarboxylative alkylations mediated by triphenylphosphine and sodium iodide
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Most photoredox catalysts in current use are precious metal complexes or synthetically elaborate organic dyes, the cost of which can impede their application for large-scale industrial processes. We found that a combination of triphenylphosphine and sodium iodide under 456-nanometer irradiation by blue light–emitting diodes can catalyze the alkylation of silyl enol ethers by decarboxylative coupling with redox-active esters in the absence of transition metals. Deaminative alkylation using Katritzky’s N-alkylpyridinium salts and trifluoromethylation using Togni’s reagent are also demonstrated. Moreover, the phosphine/iodide-based photoredox system catalyzes Minisci-type alkylation of N-heterocycles and can operate in tandem with chiral phosphoric acids to achieve high enantioselectivity in this reaction.
- Fu, Ming-Chen,Shang, Rui,Zhao, Bin,Wang, Bing,Fu, Yao
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p. 1429 - 1434
(2019/04/30)
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- Direct Photoassisted α-Trifluoromethylation of Aromatic Ketones with Trifluoroacetic Anhydride (TFAA)
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Direct α-Trifluoromethylation of acetophenone derivatives was achieved by using trifluoroacetic anhydride (TFAA) as the trifluoromethyl source and pyridine-N-oxide (Py?O) as activator and oxidant under visible light irradiation and tris-(2,2′-bipyridine)ruthenium(II) hexafluorophosphate (Ru(bpy)3(PF6)2) as the photocatalyst. Different acetophenone derivatives could be converted to the corresponding α-CF3 derivatives with high selectivity. Extensive mechanistic investigation revealed the formation of vinyl trifluoroacetate as the key intermediate for this transformation. (Figure presented.).
- Das, Somnath,Hashmi, A. Stephen K.,Schaub, Thomas
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supporting information
p. 720 - 724
(2019/01/05)
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- Visible light induced Trifluoromethyl Migration: Easy Access to α-Trifluoromethylated Ketones from Enol Triflates
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Herein, we reported a novel method to synthesize α-trifluoromethylated ketones from enol triflates. Involving a cascade sulfur dioxide extrusion and a CF3 (trifluoromethyl) radical addition process, this reaction proceeds at room temperature an
- Liu, Shuyang,Jie, Jiyang,Yu, Jipan,Yang, Xiaobo
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supporting information
p. 267 - 271
(2017/11/13)
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- Photooxidative Keto-Trifluoromethylation of Styrenes by Means of an Anthraquinone-Based Organocatalyst
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α-Trifluoromethyl ketones are versatile building blocks for the synthesis of various trifluoromethyl-functionalized molecules. Although there are significant advantages in the development of methods toward direct transformations of styrenes into α-trifluoromethyl ketones, most procedures leading to α-trifluoromethyl ketones require heavy- or transition-metal-based complexes. Herein, a novel method is developed for the synthesis of α-trifluoromethyl ketones via anthraquinone-catalyzed photooxidative keto-trifluoromethylation of styrenes with the readily available Langlois reagent (CF 3 SO 2 Na) under an oxygen atmosphere. The reactions proceed smoothly to give the products in moderate to excellent yield with good selectivity.
- Yamaguchi, Eiji,Kamito, Yuji,Matsuo, Kazuki,Ishihara, Jun,Itoh, Akichika
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p. 3161 - 3168
(2018/05/25)
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- Copper-Catalysed Decarboxylative Trifluoromethylation of β-Ketoacids
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An efficient method for Cu-catalyzed decarboxylative trifluoromethylation of β-ketoacids to achieve α-trifluoromethyl ketones was developed. A wide variety of synthetically useful α-trifluoromethyl ketones were obtained in modest to good yields under mild reaction conditions. The present method also exhibits good functional-group compatibility.
- Xu, Xiaolan,Chen, Huanhuan,He, Jianbo,Xu, Huajian
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supporting information
p. 1665 - 1668
(2017/10/05)
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- Photoredox-catalysed redox-neutral trifluoromethylation of vinyl azides for the synthesis of α-trifluoromethylated ketones
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A redox-neutral, mild, and simple protocol is developed for the synthesis of α-trifluoromethylated ketones from vinyl azides under transition-metal-free conditions. In the presence of organic photoredox catalyst N-methyl-9-mesityl acridinium and sodium trifluoromethanesulfinate, a broad range of substituted vinyl azides were found to react smoothly upon visible-light irradiation, readily furnishing the corresponding products in satisfied yields.
- Qin, Hai-Tao,Wu, Shu-Wei,Liu, Jia-Li,Liu, Feng
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p. 1696 - 1699
(2017/02/10)
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- A redox-economical synthesis of trifluoromethylated enamides with the Langlois reagent
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A redox-economical strategy for the synthesis of trifluoromethylated enamides using copper catalysis is reported. The reaction employs the inexpensive Langlois reagent (CF3SO2Na) and takes place without the need of an external oxidant. The trifluoromethylated enamide products can easily be converted into the corresponding ketone, saturated amide or oxazole.
- Yang, Hai-Bin,Selander, Nicklas
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supporting information
p. 1771 - 1775
(2017/03/08)
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- Radical Desulfur-Fragmentation and Reconstruction of Enol Triflates: Facile Access to α-Trifluoromethyl Ketones
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We report an efficient oxidative radical desulfur-fragmentation and reconstruction of enol triflates for the synthesis of α-CF3ketones. Preliminary mechanistic studies disclosed that oxidative fragmentation to release a CF3radical fr
- Su, Xiaolong,Huang, Honggui,Yuan, Yaofeng,Li, Yi
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supporting information
p. 1338 - 1341
(2017/01/24)
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- Synthesis of α-Trifluoromethylated Ketones from Vinyl Triflates in the Absence of External Trifluoromethyl Sources
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A novel method for the conversion of vinyl triflates into α-trifluoromethylated ketones in the absence of external trifluoromethyl sources is described. This process accomplishes an efficient migration of the trifluoromethyl group of the triflate to the α-position in the ketone through a radical process. The reaction proceeds by the addition of a trifluoromethyl radical to the vinyl triflate and subsequent fragmentation of the trifluoromethane sulfonyl radical. Based on this reaction, a one-pot two-step procedure for the trifluoromethylation of ketones was developed. The method presented herein also allows the transfer of perfluoroalkyl groups from vinyl perfluoroalkanesulfonates, which are readily accessible from alkynes and perfluoroalkanesulfonic acids.
- Kawamoto, Takuji,Sasaki, Rio,Kamimura, Akio
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supporting information
p. 1342 - 1345
(2017/01/24)
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- Alpha-trifluoromethyl ketone compounds and preparation method thereof
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The invention discloses a preparation method of alpha-trifluoromethyl ketone compounds and the compounds. A series of alpha-trifluoromethyl ketone compounds containing various functional groups are synthesized under conditions of room temperature and illumination. The preparation method of the alpha-trifluoromethyl ketone compounds and the compounds have the following advantages: operation is simple, raw materials are cheap and available, an application range of substrates is wide, most substrates are high in yield, and harsh reaction conditions are avoided.
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Paragraph 0026; 0027; 0028
(2018/04/01)
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- Oxidative trifluoromethylation and fluoroolefination of unactivated olefins
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Fluorine-containing organic compounds are gaining increasing importance in medicinal chemistry. Described herein is a mild and efficient method for the radical addition of olefins with TMSCF3 and TMSCF2R (R = COOEt or CF3) to deliver various α-trifluoromethylated ketones and α-fluoroolefinated ketones.
- Wu, Ye-Bin,Lu, Guo-Ping,Yuan, Tao,Xu, Zhu-Bing,Wan, Li,Cai, Chun
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supporting information
p. 13668 - 13670
(2016/11/29)
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- Manganese-Catalyzed Aerobic Oxytrifluoromethylation of Styrene Derivatives Using CF3SO2Na as the Trifluoromethyl Source
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A mild and practical protocol for manganese-catalyzed aerobic oxytrifluoromethylation of olefinic bonds of styrene derivatives using CF3SO2Na (Langlois reagent) as the CF3 source is described. A distinguishing feature of this method is the generation of trifluoromethyl radicals from CF3SO2Na using the simple manganese salt/O2 system. The reaction proceeds under ambient conditions, free of added peroxide initiators, and provides moderate to good selectivities for alcohol versus ketone product.
- Yang, Yi,Liu, Yingle,Jiang, Yan,Zhang, Yu,Vicic, David A.
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p. 6639 - 6648
(2015/10/06)
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- Direct synthesis of α-trifluoromethyl ketone from (hetero)arylacetylene: Design, intermediate trapping, and mechanistic investigations
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Regioselective addition across the alkynes has been achieved in a silver-catalyzed protocol utilizing Langlois reagent (CF3SO2Na) and molecular O2 to access medicinally active α-trifluoromethyl ketone compounds. This metho
- Maji, Arun,Hazra, Avijit,Maiti, Debabrata
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supporting information
p. 4524 - 4527
(2015/01/09)
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- A practical method for metal-free radical trifluoromethylation of styrenes with NaSO2CF3
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A mild and practical protocol for the metal-free trifluoromethylation of styrenes using NaSO2CF3 (Langlois reagent) and TBHP was developed. The approach provides efficient access to α-trifluoromethylated ketones and alcohols in moderate to good yields. Georg Thieme Verlag Stuttgart New York.
- Luo, Hai-Qing,Zhang, Zhi-Peng,Dong, Wen,Luo, Xu-Zhong
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supporting information
p. 1307 - 1311
(2014/06/10)
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- Highly efficient Cu(I)-catalyzed trifluoromethylation of aryl(heteroaryl) enol acetates with CF3 radicals derived from CF3SO 2Na and TBHP at room temperature
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An efficient method for the Cu(I)-catalyzed synthesis of α-trifluoromethyl ketones via the addition of CF3 to aryl(heteroaryl) enol acetates by using the readily available CF 3SO2Na (Langlois reagent) has been developed. The reaction is experimentally simple and carried out at room temperature, providing good to excellent yields with wide functional group tolerance.
- Lu, Yang,Li, Yaming,Zhang, Rong,Jin, Kun,Duan, Chunying
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p. 128 - 133
(2014/05/06)
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- PhI(OAc)2-mediated radical trifluoromethylation of vinyl azides with Me3SiCF3
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The fluorine-containing organic motif is becoming privileged in pharmaceuticals, agrochemicals, and functional materials, owing to its unique properties such as electron-withdrawing character, metabolic stability, and lipophilicity. Described herein is the PhI(OAc)2-mediated radical trifluoromethylation of vinyl azides with Me3SiCF3 to efficiently generate α-trifluoromethyl azines. The resulting α-trifluoromethyl azines were successfully transformed to valuable fluorine-containing molecules such as α-trifluoromethyl ketones, β-trifluoromethyl amines, 5-fluoropyrazoles, and trifluoroethyl isoquinolines. Trifluoromethylated diversity: The title reaction (see scheme) efficiently leads to α-trifluoromethyl azines, which were successfully transformed into valuable fluorine-containing molecules such as α-trifluoromethyl ketones, β-trifluoromethyl amines, 5-fluoropyrazoles, and trifluoroethyl isoquinolines. Copyright
- Wang, Yi-Feng,Lonca, Geoffroy Herve,Chiba, Shunsuke
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supporting information
p. 1067 - 1071
(2014/03/21)
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- Copper-mediated trifluoromethylation of propiolic acids: Facile synthesis of α-trifluoromethyl ketones
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Copper-mediated decarboxylative trifluoromethylation provides a new protocol for the efficient preparation of α-trifluoromethyl ketones from propiolic acids. It was found that water is involved as a reactant in the reaction, which is significantly different from the previously reported decarboxylative fluoroalkylation reactions.
- He, Zhengbiao,Zhang, Rui,Hu, Mingyou,Li, Lingchun,Ni, Chuanfa,Hu, Jinbo
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p. 3478 - 3483
(2013/11/19)
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- Sulfonation and trifluoromethylation of enol acetates with sulfonyl chlorides using visible-light photoredox catalysis
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A mild, practical method to prepare α-sulfonyl and α-trifluoromethyl ketones from readily available enol acetates and sulfonyl chlorides has been developed using visible-light photoredox catalysis. The method could be used with a wide range of enol acetates and sulfonyl chlorides, and gave the desired products in satisfactory to excellent yields. A practical method to prepare α-sulfonyl and α-trifluoromethyl ketones from enol acetates and sulfonyl chlorides using visible-light photoredox catalysis is presented. Copyright
- Jiang, Heng,Cheng, Yuanzheng,Zhang, Yan,Yu, Shouyun
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p. 5485 - 5492
(2013/09/02)
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- Oxidative trifluoromethylation of unactivated olefins: An efficient and practical synthesis of α-trifluoromethyl-substituted ketones
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An economical approach to α-CF3-substituted ketones, which are important intermediates in synthetic and medicinal chemistry, employs olefins and the readily available Langlois reagent (CF3SO 2Na). The reaction is operationally simple, proceeds at room temperature, and exhibits an excellent tolerance toward a wide variety of functional groups. Copyright
- Deb, Arghya,Manna, Srimanta,Modak, Atanu,Patra, Tuhin,Maity, Soham,Maiti, Debabrata
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supporting information
p. 9747 - 9750
(2013/09/23)
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- Photoredox catalysis: A mild, operationally simple approach to the synthesis of α-trifluoromethyl carbonyl compounds
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A facile and efficient method for the α-trifluoromethylation of carbonyl compounds and enolsilanes has been accomplished through application of a photoredox catalysis strategy. A one-flask procedure for the direct α-trifluoromethylation and α-perfluoroalk
- Pham, Phong V.,Nagib, David A.,MacMillan, David W. C.
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supporting information; experimental part
p. 6119 - 6122
(2011/08/05)
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- Generation of the CF3 radical from trifluoromethylsulfonium triflate and its trifluoromethylation of styrenes
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The CF3 radical was generated from the reaction of S-(trifluoromethyl)diphenylsulfonium triflate with Na2S 2O4 or HOCH2SO2Na under suitable conditions without further reduction. Based on this, a method for the synthesis of α-trifluoromethylated ketones has been successfully developed.
- Zhang, Cheng-Pan,Wang, Zong-Ling,Chen, Qing-Yun,Zhang, Chun-Tao,Gu, Yu-Cheng,Xiao, Ji-Chang
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p. 6632 - 6634
(2011/06/27)
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- The novel syntheses of α-trifluoromethylated ketones from β-bromoenol phosphates
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A series of 1-aryl-3,3,3-trifluro-1-propanones have been synthesized from the reaction of FO2SCF2CO2Me wilh β-bromoenol phosphates in the presence of Cul in moderate yield. The reaction mechanism was discussion, the electron-withdrawing substituent at the β-position of the enol phosphates promoted the catalytic cleavage of the O-P bond in enol phosphates by fluoride ion.
- Huang, Xiaogen,He, Yantao,Ding, Yixiang
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p. 201 - 207
(2007/10/03)
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