- Copper-mediated pentafluoroethylation of organoboronates and terminal alkynes with TMSCF3
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The TMSCF3-derived CuCF2CF3 species has been successfully applied in pentafluoroethylation of organoboronates and terminal alkynes. By using 1,10-phenanthroline as a ligand, a broad range of (hetero)arylboronates and alkenylboronates were smoothly pentafluoroethylated under aerobic conditions. Furthermore, terminal alkynes can undergo aerobic cross-coupling with the TMSCF3-derived CuCF2CF3 species in the absence of additional ligands.
- Pan, Shitao,Xie, Qiqiang,Wang, Xiu,Wang, Qian,Ni, Chuanfa,Hu, Jinbo
-
supporting information
p. 5156 - 5159
(2022/04/21)
-
- Solvated Nickel Complexes as Stoichiometric and Catalytic Perfluoroalkylation Agents**
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The acetonitrile-solvated [(MeCN)Ni(C2F5)3]? was prepared in order to compare and contrast its reactivity with the known [(MeCN)Ni(CF3)3]? towards organic electrophiles. Both [(MeCN)Ni(CF3)3]? and [(MeCN)Ni(C2F5)3]? successfully react with aryl iodonium and diazonium salts as well as alkynyl iodonium salts to give fluoroalkylated organic products. Electrochemical analysis of [(MeCN)NiII(C2F5)3]? suggests that, upon electro-oxidation to [(MeCN)nNiIII(C2F5)3], reductive homolysis of a perfluoroethyl radical occurs, with the concomitant formation of [(MeCN)2NiII(C2F5)2]. Catalytic C?H trifluoromethylations of electron-rich arenes were successfully achieved using either [(MeCN)Ni(CF3)3]? or the related [Ni(CF3)4]2?. Stoichiometric reactions of the solvated nickel complexes reveal that “ligandless” nickel is exceptionally capable of serving as reservoir of CF3 groups under catalytically relevant conditions.
- Shreiber, Scott T.,Vicic, David A.
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supporting information
p. 18162 - 18167
(2021/07/14)
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- NOVEL METHOD FOR PRODUCING PERFLUOROALKYLATING AGENTS USING MONOHYDROPERFLUOROALKANE AS STARTING MATERIAL, AND METHOD FOR PRODUCING AROMATIC PERFLUOROALKYL COMPOUNDS USING THE SAME
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To provide a simple method for producing silylated trifluoromethylcarbinol from trifluoromethane.SOLUTION: There is provided a method for producing a compound represented by the formula [1], in which the compound is obtained by reacting a monohydroperfluoroalkane, a carbonyl compound, and NaH in an organic solvent and then reacting the reaction solution with a silylating agent. [In the formula, RF is an alkyl group such as a linear chain of C1 to 2, and a perfluoroalkyl group in which all H on C is substituted with F; R1 and R2 are independently alkyl groups such as a linear chain of H or C1 to 2, or the like respectively; R1 and R2 may be integrated to form a ring; and R3, R4 and R5 are independently H or C1 to 2 linear alkyl groups, or the like respectively.]SELECTED DRAWING: None
- -
-
Paragraph 0135-0138
(2021/04/02)
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- NOVEL METHOD FOR PRODUCING PERFLUOROALKYLATING AGENTS USING MONOHYDROPERFLUOROALKANE AS STARTING MATERIAL, AND METHOD FOR PRODUCING AROMATIC PERFLUOROALKYL COMPOUND USING THE SAME
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PROBLEM TO BE SOLVED: To provide a simple method for producing trifluoromethyltriol borate potassium from trifluoromethane. SOLUTION: There is provided a method for producing a compound represented by the formula [7], comprising: reacting a monohydroperfluoroalkane with a base and trialkyl borate in an organic solvent; and then reacting the reaction solution with triol. [In the formula, RF is an alkyl group such as a linear chain of C1-2, and a perfluoroalkyl group in which all H on C is substituted with F; R6 is H or a C1-2 linear alkyl group, or the like; M may be a metal or the like belonging to Group I, Group II, Group III, Group IV, Group V, Group VI, Group VII, Group VIII, Group IX, Group X, Group XI, Group XII, and Group XIII in the periodic table of elements, and they may be a single substance or a mixture of a plurality of substances and y corresponds to the oxidation number of the substance represented by M.] SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
- -
-
Paragraph 0135-0138; 0140
(2021/04/09)
-
- NOVEL METHOD FOR PRODUCING PERFLUOROALKYLATING AGENTS USING MONOHYDROPERFLUOROALKANE AS STARTING MATERIAL, AND METHOD FOR PRODUCING AROMATIC PERFLUOROALKYL COMPOUND USING THE SAME
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PROBLEM TO BE SOLVED: To provide a method for producing an aromatic perfluoroalkyl compound using silylated trifluoromethyl carbinol. SOLUTION: There is provided a method for producing an aromatic perfluoroalkyl compound represented by the general formula [10], in which a compound represented by the formula [9] and a compound represented by the formula [1] are reacted in an organic solvent in the presence of a copper catalyst, a nitrogen ligand and a metal fluoride. R7-X...[9], RF-R7...[10] [In the formula, R7 is an aryl group or the like which may have a substituent; X is F, Cl, Br or I; RF is an alkyl group such as a linear chain of C1-2, and a perfluoroalkyl group in which all H on C is substituted with F; R1 and R2 are each independently H or a C1-2 linear alkyl group, or the like; R1 and R2 may be integrated to form a ring; and R3, R4 and R5 are each independently H or a C1-2 linear alkyl group, or the like.] SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
- -
-
Paragraph 0135-0138; 0140
(2021/04/09)
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- Pentafluoroethylation of Arenediazonium Tetrafluoroborates Using On-Site Generated Tetrafluoroethylene
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Copper-mediated pentafluoroethylation of arenediazonium tetrafluoroborates with tetrafluoroethylene (TFE) on-site generated from TMSCF3 has been developed as a new method to prepare pentafluoroethyl arenes. The active pentafluoroethylation reagent “CuC2F5” is pre-generated from CuSCN, TFE and CsF, and its generation and further reaction are strongly solvent-dependent. This pentafluoroethylation reaction represents the first example of Sandmeyer-type pentafluoroethylation, which exhibits good functional group tolerance and potential applications for the synthesis of complicated bioactive compounds.
- Xing, Bo,Li, Lingchun,Ni, Chuanfa,Hu, Jinbo
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p. 1131 - 1136
(2019/10/22)
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- "ligandless" Pentafluoroethylation of Unactivated (Hetero)aryl and Alkenyl Halides Enabled by the Controlled Self-Condensation of TMSCF3-Derived CuCF3
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Pentafluoroethylation of unactivated C(sp2)-X bonds (X = I, Br) using a storable, "ligandless" CuC2F5 reagent prepared by controlled self-condensation of ready available TMSCF3-derived CuCF3 has been
- Mestre, Jordi,Castillón, Sergio,Boutureira, Omar
-
supporting information
p. 15087 - 15097
(2019/11/03)
-
- NEW MANUFACTURING METHOD OF PERFLUORO ALKYLATING AGENT WHICH USED MONOHYDROPERFLUOROALKANE AS STARTING MATERIAL, AND METHOD FOR MANUFACTURING AROMATIC PERFLUORO ALKYL COMPOUND USING THE SAME
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PROBLEM TO BE SOLVED: To provide a method for manufacturing silanized trifluoromethyl carbinol, potassium trifluoromethyl triol borate and an aromatic trifluoromethyl compound from trifluoromethane. SOLUTION: There are provided a method for manufacturing silanized trifluoromethyl carbinol in which trifluoromethyl carbinol obtained by reacting trifluoromethane with a carbonyl compound in the presence of a base is reacted with silanizing agent; or a method for manufacturing potassium trifluoromethyl triol borate in which potassium trifluoromethyl trimethoxy borate obtained by reacting trifluoromethane with trimethoxy borane in the presence of a base is reacted with a triol; and a method for manufacturing an aromatic trifluoromethyl compound obtained by making an aromatic iodide act on silanized trifluoromethyl carbinol or potassium trifluoromethyl triol borate in the presence of catalytic amount of copper (I) iodide and 9,10-phenanthroline. SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
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-
Paragraph 0135; 0136
(2018/12/14)
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- CuI-Catalyzed Pentafluoroethylation of Aryl Iodides in the Presence of Tetrafluoroethylene and Cesium Fluoride: Determining the Route to the Key Pentafluoroethyl CuI Intermediate
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The Cu(I)-catalyzed pentafluoroethylation of iodoarenes via the fluorocupration of tetrafluoroethylene (TFE) is disclosed. The active species, (phen)CuC2F5, was isolated and its molecular structure confirmed by a single-crystal X-ray diffraction analysis. The key to the successful suppression of the competing oligomerization of TFE is to refrain from stirring the reaction mixture. A mechanistic study clearly discarded the possibility that the catalytic reaction proceeds via a radical pathway.
- Ohashi, Masato,Ishida, Naoyoshi,Ando, Kota,Hashimoto, Yu,Shigaki, Anna,Kikushima, Kotaro,Ogoshi, Sensuke
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supporting information
p. 9794 - 9798
(2018/07/25)
-
- From C1 to C2: TMSCF3 as a Precursor for Pentafluoroethylation
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A highly efficient copper-mediated aromatic pentafluoroethylation method using TMSCF3 as the sole fluoroalkyl source is described. The reaction proceeds by a key C1 to C2 process, that is, the generation of CuCF3 from TMSCF3, followed by a subsequent spontaneous transformation into CuC2F5. Various aryl iodides were pentafluoroethylated with the TMSCF3-derived CuC2F5. This method represents the first practical and efficient method for pentafluoroethylation of aryl iodides using commercially available TMSCF3 as a pentafluoroethyl precursor.
- Xie, Qiqiang,Li, Lingchun,Zhu, Ziyue,Zhang, Rongyi,Ni, Chuanfa,Hu, Jinbo
-
supporting information
p. 13211 - 13215
(2018/09/25)
-
- TMSCF3 as a Convenient Source of CF2=CF2 for Pentafluoroethylation, (Aryloxy)tetrafluoroethylation, and Tetrafluoroethylation
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A new method for the on-site preparation of tetrafluoroethylene (TFE) and a procedure for its efficient use in pentafluoroethylation by fluoride addition were developed by using a simple two-chamber system. The on-site preparation of TFE was accomplished by dimerization of difluorocarbene derived from (trifluoromethyl)trimethylsilane (TMSCF3) under mild conditions. Other fluoroalkylation reactions, such as (aryloxy)tetrafluoroethylation and tetrafluoroethylation processes, were also achieved using a similar approach. This work not only demonstrates a convenient and safe approach for the generation and use of TFE in academic laboratories, but also provides a new strategy for pentafluoroethylation.
- Li, Lingchun,Ni, Chuanfa,Xie, Qiqiang,Hu, Mingyou,Wang, Fei,Hu, Jinbo
-
supporting information
p. 9971 - 9975
(2017/08/08)
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- A Convenient Method for Catalytic Aromatic Pentafluoroethylation Using Potassium (Pentafluoroethyl)trimethoxyborate
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A method for the copper-catalyzed pentafluoroethylation of aryl iodides using potassium (pentafluoroethyl)trimethoxyborate has been developed. The borate was found to be a convenient pentafluoroethyl source. In parallel, it was found that the solvent, as well as ligand, makes significant impact on the catalytic perfluoroalkylations.
- Sugiishi, Tsuyuka,Kawauchi, Daisuke,Sato, Mizuki,Sakai, Tatsuya,Amii, Hideki
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p. 1874 - 1878
(2017/04/06)
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- Pentafluoroethylbenziodoxole (BIX-C2F5): A Shelf-Stable Reagent for Pentafluoroethylation of β-Ketoesters and Arylboronic Acids
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An improved method for the preparation of pentafluoroethylating reagent pentafluoroethyl-substituted benziodoxole (BIX-C2F5) was described. Under mild conditions, BIX-C2F5was able to react with β-ketoesters or aryl/heteroaryl boronic acids to generate pentafluoroethylated compounds in good yields.
- Zhu, Jiansheng,Li, Yuguang,Ni, Chuanfa,Shen, Qilong
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p. 662 - 668
(2016/07/22)
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- Stable but reactive perfluoroalkylzinc reagents: Application in ligand-free copper-catalyzed perfluoroalkylation of aryl iodides
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The aromatic perfluoroalkylation catalyzed by a copper(I) salt with bis(perfluoroalkyl)zinc reagents Zn(RF)2(DMPU)2, which were prepared and then isolated as a stable white powder from perfluoroalkyl iodide and diethylzinc, was accomplished to provide the perfluoroalkylated products in good-to-excellent yields. The advantages of this reliable and practical catalytic reaction are 1) airstable and easy-to-handle bis(perfluoroalkyl)zinc reagents can be utilized, 2) the reagent is reactive and hence the operation without activators and ligands is simple, and 3) not only trifluoromethylation but also perfluoroalkylation can be attained.
- Aikawa, Kohsuke,Nakamura, Yuzo,Yokota, Yuki,Toya, Wataru,Mikami, Koichi
-
supporting information
p. 96 - 100
(2015/02/05)
-
- Pentafluoroethylating compositions
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The present invention relates to pentafluoroethylating compositions, processes for obtaining them, and their use in pentafluoroethylation reactions.
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-
Paragraph 0195
(2015/02/25)
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- PENTAFLUOROETHYLATING COMPOSITIONS
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The present invention relates to pentafluoroethylating compositions, processes for obtaining them, and their use in pentafluoroethylation reactions.
- -
-
Page/Page column 37; 38; 39
(2015/02/25)
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- Diversity-oriented approach to CF3CHF-, CF3CFBr-, CF3CF2-, (CF3)2CH-, and CF3(SCF3)CH-substituted arenes from 1-(Diazo-2,2,2-trifluoroethyl)arenes
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Arenes substituted with perfluoroalkyl groups are attractive targets for drug and agrochemical development. Exploiting the carbenic character of donor/acceptor diazo compounds, a diversity-oriented synthesis of perfluoroalkylated arenes, for late stage fluorofunctionalization, is described. The reaction of 1-(diazo-2,2,2-trifluoroethyl)arenes with HF, F/Br, F2, CF3H, and CF3SH sources give direct access to a variety of perfluoroalkyl-substituted arenes presenting with incremental fluorine content. The value of this approach is also demonstrated for radiochemistry and positron emission tomography with the [18F]-labeling of CF3CHF-, CF3CBrF-, and CF3CF2-arenes from [18F]fluoride.
- Emer, Enrico,Twilton, Jack,Tredwell, Matthew,Calderwood, Samuel,Collier, Thomas Lee,Ligault, Benot,Taillefer, Marc,Gouverneur, Vronique
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p. 6004 - 6007
(2015/01/09)
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- Direct synthesis of pentafluoroethyl copper from pentafluoropropionate as an economical C2F5 source: Application to pentafluoroethylation of arylboronic acids and aryl bromides
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The direct synthesis of pentafluoroethyl copper (CuC2F 5) from a cuprate reagent and ethyl pentafluoropropionate as one of the most economical and useful pentafluoroethyl sources was accomplished. The advantages of this method are; all the reagents employed are low-cost and operationally simple, and the CuC2F5 reagent is prepared in virtually quantitative yield. Furthermore, the CuC2F5 reagent prepared was successfully applied to two types of pentafluoroethylations with arylboronic acids and aryl bromides to provide the pentafluoroethylated aromatic products in good-to-excellent yields, including large scale operations.
- Serizawa, Hiroki,Aikawa, Kohsuke,Mikami, Koichi
-
supporting information
p. 3456 - 3459
(2014/07/21)
-
- Cupration of C2F5H: Isolation, structure, and synthetic applications of [K(DMF)2][(t -BuO)Cu(C2F 5)]. Highly efficient pentafluoroethylation of unactivated aryl bromides
-
Pentafluoroethane, C2F5H (HFC-125), is smoothly cuprated with preisolated or in situ-generated [K(DMF)][(t-BuO)2Cu] to give [K(DMF)2][(t-BuO)Cu(C2F5)] (1) in nearly quantitative yield. Complex 1 has been isolated, structurally characterized, and demonstrated to be an exceedingly versatile pentafluoroethylating reagent for a variety of substrates, including unactivated aryl bromides.
- Lishchynskyi, Anton,Grushin, Vladimir V.
-
supporting information
p. 12584 - 12587
(2013/09/23)
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- The solid complex Zn(CF3)Br·2DMF as an alternative reagent for the preparation of both, trifluoromethyl and pentafluoroethyl copper, CuCF3 and CuC2F5
-
Trifluoromethylcopper and pentafluoroethylcopper are prepared conveniently via the reaction of the solid complex Zn(CF3)Br·2DMF with copper(I) bromide in N,N-dimethylformamide. The reactions of both copper species with 2,4-dinitrochlorobenzene,
- Kremlev, Mikhail M.,Tyrra, Wieland,Mushta, Aleksej I.,Naumann, Dieter,Yagupolskii, Yurii L.
-
experimental part
p. 212 - 216
(2010/04/30)
-
- Substituted cyclohexylaminopyrimidines
-
Compounds of formula I where R1is hydrogen, chlorine, fluorine or methyl, R2and R3, which may be the same or different from each other, are hydrogen, halogen, cyano, (C1-C4)-alkyl, vinyl, ethynyl, (C
- -
-
-
- A NOVEL AND CONVENIENT METHOD FOR TRIFLUOROMETHYLATION OF ORGANIC HALIDES USING CF3SiR'3/KF/Cu(I) SYSTEM
-
Fluoride ion induced cross-coupling reaction of organic halides with trifluoromethyltrialkylsilanes takes place in the presence of Cu(I) salts under mild reaction conditions to give the corresponding trifluoromethylated products in high yields.
- Urata, Hisao,Fuchikami, Takamasa
-
-
- THE TRIFLUOROMETHYLATION OF CHLOROAROMATICS USING THE COPPER-CF2Br2-DIALKYLAMIDE REACTION SYSTEM
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The in situ generation of CuCF3 from the reaction of copper, dibromodifluoromethane and either N,N-dimethylformamide or N,N-dimethylacetamide (Burton's reagent) has been used for the direct substitution of chlorine by CF3 in a number of aromatic substrates.Particular attention has been paid to the effects of ring substituents on the efficiency of reaction.
- Clark, James H.,Denness, James E.,McClinton, Martin A.,Wynd, Andrew J.
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p. 411 - 426
(2007/10/02)
-
- A CONVENIENT SYNTHESIS OF PENTAFLUOROETHYL-SUBSTITUTED AROMATICS
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The reaction of substituted aryl bromides and iodides with potassium pentafluoropropionate and copper (I) iodide in DMF/toluene at 150 deg C gives good yields of the corresponding aryl pentafluoroethyl compounds.
- Freskos, John N.
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p. 965 - 972
(2007/10/02)
-
- Sodium Perfluoroalkane Carboxylates as Sources of Perfluoroalkyl Groups
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Sodium trifluoroacetate, in the presence of copper(I) iodide, is used as a source of trifluoromethyl to replace halogen by trifluoromethyl in benzenoid and heterocyclic aromatic systems, as well as in alkenyl and alkyl halogen compounds.The mechanism of this interesting copper-assisted process has been explored and an intermediate of the form - is proposed.Introduction of higher perfluoroalkyl groups from their respective sodium perfluoroalkane carboxylates has been demonstrated and the machanistic features are compared with those of the trifluoromethylation process.
- Carr, Gillian E.,Chambers, Richard D.,Holmes, Thomas F.,Parker, David G.
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p. 921 - 926
(2007/10/02)
-
- Studies on Organic Fluorine Compounds. Part 27. Abnormal Reactions in the Trifluoromethylation of Aromatic Compounds with Trifluoromethyl Iodide and Copper Powder
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Reaction of 3-bromobenzofuran with trifluoromethyl iodide and copper powder in pyridine gave 2-(trifluoromethyl)-, 2- and 3-(pentafluoroethyl)-, and 2,3-bis(trifluoromethyl)-benzofuran, as well as the expected product, 3-(trifluoromethyl)benzofuran.Bromoanisole also gave (trifluoromethyl)anisole and (pentafluoroethyl)anisole, but introduction of the perfluoroalkyl group occurred at the position originally occupied by the bromine.Formation of pentafluoroethyl compounds is explained by decomposition of trifluoromethylcopper to cuprous fluoride and difluorocarbene, which can then react with a further molecule of trifluoromethylcopper to form pentafluoroethylcopper.This then reacts with aryl halide to give pentafluoroethyl compounds.Perfluoroalkylcopper is thermally cleaved to perfluoroalkyl radical, which then reacts with pyridine to give perfluoroalkylpyridines.This mechanism must be involved in the formation of 2,3-bis(trifluoromethyl)benzofuran.Introduction of a perfluoroalkyl group to the position originally unoccupied with halogen might be due to the rather localized double bond in benzofuran.
- Kobayashi, Yoshiro,Kumadaki, Itsumaro
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p. 661 - 664
(2007/10/02)
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