- Selectivity and Charge Transfer in Photoreactions of α,α,α-Trifluorotoluene with Olefins
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In photoreactions of α,α,α-trifluorotoluene with olefins, the mode of reaction strongly depends on the charge transfer between the starting materials.Substitution of an F-atom is prefferred if the electron transfer becomes exergonic, i.e. if ΔG 0 accord
- Mattay, Jochen,Runsink, Jan,Gersdorf, Joachim,Rumbach, Thomas,Ly, Cuong
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- Silver-catalyzed decarboxylative radical allylation of α,α-difluoroarylacetic acids for the construction of CF2-allyl bonds
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An efficient silver-catalyzed method of decarboxylative radical allylation of α,α-difluoroarylacetic acids to build CF2-allyl bonds has been developed. Using allylsulfone as an allyl donor, α,α-difluorine substituted arylacetic acids bearing various functional groups are successfully allylated to access a series of 3-(α,α-difluorobenzyl)-1-propylene compounds in moderate to excellent yields in aqueous CH3CN solution under the mild conditions. Experimental studies disclosed that the α-fluorine substitution of arylacetic acid has a great influence on free radical activity and reactivity.
- Wang, Pingyang,Du, Pengcheng,Sun, Qianqian,Zhang, Jianhua,Deng, Hongmei,Jiang, Haizhen
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p. 2023 - 2029
(2021/03/16)
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- Silver-catalyzed decarboxylative homocoupling reaction for the construction of tetrafluoroethylene-bridging aromatic compounds
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The Ag(I)-catalyzed decarboxylative homocoupling from the difluoroacetate has been developed to the synthesis of symmetric CF2–CF2 containing dimers. This radical dimerization overpasses the prefunctionalization of the substrate and provides a direct and efficient method for construction of tetrafluoroethylene bridge-linked homodimers.
- Wang, Yong,Zhao, Huaxin,Xie, Xiaojuan,Jiang, Haizhen,Deng, Hongmei,Hao, Jian,Wan, Wen
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supporting information
p. 2961 - 2970
(2019/08/22)
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- The Versatile Behavior of Platinum Alkyne Complexes towards XeF2: Formation of Fluorovinyl and Fluorido Complexes
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Reactions of platinum(0) tolane complexes, bearing a chelating ligand with P and N donor atoms, with the electrophilic fluorinating agent XeF2 give facile access to platinum(II) β-fluorovinyl fluorido complexes. A series of new platinum(II) β-fluorovinyl complexes have been synthesized and were structurally characterized. Further oxidation with XeF2 led to ortho-metalated platinum(IV) fluorido compounds. Additional reactions of platinum(0) tolane complexes, bearing a chelating P,P donor ligand, with XeF2 led to a variety of fluorido and fluorovinyl complexes.
- Berger, Josefine,Braun, Thomas,Ahrens, Theresia,Kl?ring, Paul,Laubenstein, Reik,Braun-Cula, Beatrice
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p. 8886 - 8900
(2017/07/11)
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- Silver-Catalyzed Decarboxylative Alkynylation of α,α-Difluoroarylacetic Acids with Ethynylbenziodoxolone Reagents
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A decarboxylating alkynylation of α,α-difluoroarylacetic acids with ethynylbenziodoxolone reagents is reported. AgNO3 serves as the catalyst and K2S2O8 as the oxidant. A series of functional groups were tolerated, and moderate to good yields were obtained.
- Chen, Fei,Hashmi, A. Stephen K.
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p. 2880 - 2882
(2016/07/06)
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- FLUORINE-CONTAINING COMPLEX COMPOUND, AND PRODUCTION METHOD FOR FLUORINE-CONTAINING ORGANIC COMPOUND EMPLOYING SAME
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An object of the present invention is to enable the synthesis of various fluorine-containing compounds having an organic group at both terminals of their tetrafluoroethylene structure (—CF2—CF2—). The present invention provides a flu
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Paragraph 0297; 0298
(2016/08/17)
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- Copper(0)-mediated fluoroalkylation of iodobenzene with 2-bromo-1,1,2,2-tetrafluoroethyl compounds: Investigation on the influence of R substituent on the reactivity of RCF2Cu species
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We have made a systematic investigation on the copper(0)-mediated tetrafluoroethylenation of iodobenzene with structurally diverse 2-bromo-1,1,2,2-tetrafluoroethyl compounds. A comparison of this reaction with 1,2,2-trifluoro-1-phenylethylation and the known functionalized difluoroalkylation demonstrates that the substituent R of α,α-difluoroalkyl copper species RCF2Cu plays a crucial role on their reactivity, which is believed to be useful for the development of new fluoroalkylation reactions under the promotion of transition metals.
- Zhu, Jieming,Ni, Chuanfa,Gao, Bing,Hu, Jinbo
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p. 139 - 147
(2015/03/04)
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- A clean and selective radical homocoupling employing carboxylic acids with titania photoredox catalysis
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A titania photoredox catalysis protocol was developed for the homocoupling of C-centered radicals derived from carboxylic acids. Intermolecular reactions were generally efficient and selective, furnishing the desired dimers in good yields under mild neutral conditions. Selective cross-coupling with two acids proved unsuccessful. An intra-molecular adaptation enabled macrocycles to be prepared, albeit in modest yields. (Chemical Equation Presented).
- Manley, David W.,Walton, John C.
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supporting information
p. 5394 - 5397
(2015/02/19)
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- Fluoroalkylcopper(I) complexes generated by the carbocupration of tetrafluoroethylene: Construction of a tetrafluoroethylene-bridging structure
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We report a copper-mediated synthesis of a variety of 1,2-difunctionalized-1,1,2,2-tetrafluoroethylene derivatives via the carbocupration of tetrafluoroethylene. The key synthetic intermediates, 2-aryl-1,1,2,2-tetrafluoroethylcopper complexes, can be easily prepared, stored, and used as fluoroalkylation reagents. The molecular structure was unambiguously determined by X-ray crystallography and NMR analysis. We applied this method to the short-step synthesis of a liquid-crystalline compound bearing a tetrafluoroethylene-bridging structure.
- Saijo, Hiroki,Ohashi, Masato,Ogoshi, Sensuke
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supporting information
p. 15158 - 15161
(2014/12/11)
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- Arylsulfur chlorotetrafluorides as useful fluorinating agents: Deoxo- and dethioxo-fluorinations
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Usage of arylsulfur chlorotetrafluorides 1 as versatile deoxo- and dethioxo-fluorinating agents is described. There have been developed two convenient methods for the in situ preparation of reactive arylsulfur trifluorides 2 from 1. The one is reduction of 1 with a reducer such as pyridine to 2, and the other is disproportionation of 1 with a diaryl disulfide to 2 with evolution of chlorine gas. The latter method is a convenient way to get neat 2 from 1. The in situ prepared 2 fluorinates many kinds of substrates such as alcohols, aldehydes, ketones, diketones, and carboxylic acids to give the corresponding CF, CF2, CF2CF2, and CF 3 compounds in high yields. 2 also fluorinates various sulfur compounds including CS groups to give CF2, OCF2, CF 3, and OCF3 compounds in high yields. Reactions of 2 with diols or bis(trimethylsilyl) derivatives of diols or amino alcohols provided the corresponding deoxofluoro-arylsulfinylation products in high yields. In addition, it has been found that chlorotetrafluorides 1 directly and effectively react with the sulfur compounds to give the corresponding fluoro compounds in high yields. Since they are the intermediates for the production of industrially useful arylsulfur pentafluorides, arylsulfur chlorotetrafluorides 1, in particular, phenylsulfur chlorotetrafluoride (1a) are expected to find use as inexpensive and versatile deoxo- and dethioxo-fluorinating agents for the preparation of many organofluoro compounds.
- Umemoto, Teruo,Singh, Rajendra P.
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experimental part
p. 17 - 27
(2012/09/07)
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- Direct addition of fluorine to arylacetylenes
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Under suitable conditions elemental fluorine can be added across the carbon-carbon triple bond of arylacetylenes forming tetrafluoroethane derivatives - ArCF2CF2R - in good yields.
- Gatenyo, Julia,Rozen, Shlomo
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experimental part
p. 332 - 335
(2009/12/03)
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- Direct nucleophilic fluorination of carbonyl groups of benzophenones and benzils with Deoxofluor
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The carbonyl groups of diaryl ketones and diaryl diketones were directly fluorinated with bis(2-methoxyethyl)aminosulfur trifluoride (Deoxofluor) under neat conditions to give the corresponding gem-difluorides and tetrafluorinated derivatives in moderate
- Chang, Ying,Tewari, Amit,Adi, Avi-Izak,Bae, Chulsung
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p. 9837 - 9842
(2008/12/22)
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- Nucleophilic di- and tetrafluorination of dicarbonyl compounds
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Reactions of various diketo compounds with Deoxofluor [(CH3OCH2CH2)2NSF3] have been investigated. When reacted with Deoxofluor, α-diketones, R1COCOR2 (R1 = R2/su
- Singh,Majumder,Shreeve
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p. 6263 - 6267
(2007/10/03)
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- ARYLPOLYFLUOROOLEFIN OXIDES.III. TRANS-α,β-DIFLUOROSTILBENE OXIDE AND ITS REACTIONS
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1,2-Diphenyl-1,2-difluoro-1,2-epoxyethane was obtained by the oxidation of trans α,β-difluorostilbene with oxygen in the presence of chlorine or by the action of perbenzoic acid.The reaction of 1,2-diphenyl-1,2-difluoro-1,2-epoxyethane with cesium fluoride and also its thermolysis lead to α,α-difluorobenzyl phenyl ketone.In reaction with methanol α,β-difluorostilbene oxide forms a diphenyl-α,β-diketone, while sulfur tetrafluoride fluorinates it to 1,2-diphenyltetrafluoroethane.
- Kremlev, M. M.,Maznyi, I. S.,Sereda, S. V.,Yagupol'skii, Yu. L.
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p. 758 - 761
(2007/10/02)
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- A Novel Method for Constructing a CF2 Group via the Reaction of Alkynes with BrF and IF Prepared Directly from the Corresponding Elements
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The molecules of IF and BrF as entities, prepared from the respective elements, have practically never been used in organic chemistry.When reacted with various types of alkynes the unknown family of compounds containing CF2CX2 (X=I,Br) was obtained in good yields.With phenylacetylenes an additional substitution of one or both X atoms by fluorine was observed.Very deactivated triple bonds, such as 23 and 25, react successfully only with BrF.Since the starting material is F2 and most reactions are fast, this method should be suitable for synthesis of biologicallyinteresting 18F-containing compounds.The main method used previously for introducing the elements of XF into organic molecules, namely with N-halo amides-anhydrous HF, is not suitable for reaction with alkynes.
- Rozen, Shlomo,Brand, Michael
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p. 222 - 225
(2007/10/02)
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