- Catalytic trifluoromethylation of iodoarenes by use of 2-trifluoromethylated benzimidazoline as trifluoromethylating reagent
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The trifluoromethylation of iodoarenes was accomplished by use of a 2-trifluoromethylbenzimidazoline derivative as the trifluoromethylating reagent and a catalytic amount of Cu(I) in the presence of 2,2'-bipyridyl as the ligand. Through a mechanistic study, we found that the oxidative addition of the iodoarene to the Cu(I)–CF3 species is the rate-determining step.
- Akiyama, Takahiko,Ishikawa, Taisuke,Kamiyama, Nanami,Uchikura, Tatsuhiro
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supporting information
p. 2442 - 2447
(2020/11/07)
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- A radical approach to the copper oxidative addition problem: Trifluoromethylation of bromoarenes
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Transition metal–catalyzed arene functionalization has been widely used for molecular synthesis over the past century. In this arena, copper catalysis has long been considered a privileged platform due to the propensity of high-valent copper to undergo reductive elimination with a wide variety of coupling fragments. However, the sluggish nature of oxidative addition has limited copper’s capacity to broadly facilitate haloarene coupling protocols. Here, we demonstrate that this copper oxidative addition problem can be overcome with an aryl radical–capture mechanism, wherein the aryl radical is generated through a silyl radical halogen abstraction. This strategy was applied to a general trifluoromethylation of aryl bromides through dual copper-photoredox catalysis. Mechanistic studies support the formation of an open-shell aryl species.
- Le, Chip,Chen, Tiffany Q.,Liang, Tao,Zhang, Patricia,MacMillan, David W. C.
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p. 1010 - 1014
(2018/06/12)
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- Phosphovanadomolybdic acid catalyzed direct C-H trifluoromethylation of (hetero)arenes using NaSO2CF3 as the CF3 source and O2 as the terminal oxidant
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A direct C-H trifluoromethylation of (hetero)arenes using NaSO2CF3 (Langlois' reagent) as the CF3 source and O2 as the terminal oxidant has been developed. In the presence of catalytic amounts of phosphovanadomolybdic acids, such as H6PV3Mo9O40, various kinds of substituted benzenes and heteroaromatic compounds could be converted into the corresponding trifluoromethylated products.
- Li, Chifeng,Suzuki, Kosuke,Yamaguchi, Kazuya,Mizuno, Noritaka
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supporting information
p. 1417 - 1420
(2017/02/23)
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- Trifluoromethylation of (hetero)aryl iodides and bromides with copper(i) chlorodifluoroacetate complexes
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A new copper-mediated trifluoromethylation reaction using copper(i) chlorodifluoroacetate complexes as reagents is reported. The complex [L2Cu][O2CCF2Cl] (L = bpy, dmbpy, phen) reacted with (hetero)aryl iodides and bromides in the presence of CsF in DMF at 75 °C to afford the trifluoromethylarenes in good to excellent yields. High compatibility with various chemical functions or (hetero)cycles was also observed in the reaction. A reaction mechanism involving a difluorocarbene intermediate, along with a subsequent formation of a -CF3 anion was proposed.
- Lin, Xiaoxi,Li, Zhengyu,Han, Xiaoyan,Weng, Zhiqiang
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p. 75465 - 75469
(2016/08/24)
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- TCDA: Practical Synthesis and Application in the Trifluoromethylation of Arenes and Heteroarenes
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A practical synthesis of the reagent trimethylsilyl chlorodifluoroacetate (TCDA) is reported on 50 g scale. The trifluoromethylation with TCDA was optimized, and the reaction shows very broad scope with respect to electron-deficient, -neutral, -rich aryl/heteroaryl iodides, as well as excellent functional group tolerability, such as ester, amide, aldehyde, hydroxyl, and carboxylic acid. The reagent was also applied to the late-stage trifluoromethylation of three medicinally relevant compounds. Additionally, the building block trifluoromethylpyridine and one drug related molecule Boc-Fluoxetin were synthesized in 10 g scale by this method, demonstrating its practical applications in process chemistry.
- Wang, Jian,Zhang, Xiaomin,Wan, Zehong,Ren, Feng
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p. 836 - 839
(2016/05/19)
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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
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supporting information
p. 96 - 100
(2015/02/05)
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- New Reagent for Highly Efficient Synthesis of Trifluoromethyl-Substituted Arenes and Heteroarenes
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A new reagent trimethylsilyl chlorodifluoroacetate (TCDA) is reported for the introduction of a -CF3 group to arenes and heteroarenes. Compared with current known reagents, TCDA shows very broad scope with respect to electron-deficient, -neutral, and -rich aryl/heteroaryl iodides as well as excellent functional group tolerance, including ester, amide, aldehyde, hydroxyl, and carboxylic acid. (Chemical Equation Presented).
- Zhang, Xiaomin,Wang, Jian,Wan, Zehong
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supporting information
p. 2086 - 2089
(2015/05/13)
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- BIS(TRIFLUOROMETHYL)ZINC DMPU COMPLEX, MANUFACTURING METHOD THEREOF AND MANUFACTURING METHOD OF TRIFLUOROMETHYL GROUP-CONTAINING COMPOUND USING THE SAME
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PROBLEM TO BE SOLVED: To provide a bis(trifluoromethyl)zinc DMPU complex stable under room temperature and useful as a reaction reagent, a manufacturing method thereof and a manufacturing method of a trifluoromethyl group-containing compound using the same. SOLUTION: A method of obtaining a trifluoromethyl group-containing compound by reacting with a substituted aromatic iodide under a copper (I) catalyst after obtaining a bis(fluoromethyl)zinc DMPU complex represented by the formula (1) (CF3)2Zn (DMPU)2 (1), where DMPU represents N,N'-dimethyl propylene urea, by reacting dialkyl zinc, trifluoromethyl halide and N,N'-dimethyl propylene urea in an organic solvent, then filtration or solvent leaving removal of precipitate. COPYRIGHT: (C)2015,JPOandINPIT
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Paragraph 0027-0029
(2018/11/22)
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- Efficient copper-catalyzed trifluoromethylation of aromatic and heteroaromatic iodides: The beneficial anchoring effect of borates
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Efficient copper-catalyzed trifluoromethylation of aromatic iodides was achieved with TMSCF3 in the presence of trimethylborate. The Lewis acid was used to anchor the in situ generated trifluoromethyl anion and suppress its rapid decomposition. Broad applicability of the new trifluoromethylating reaction was demonstrated in the functionalization of different aromatic and heteroaromatic iodides.
- Gonda, Zsombor,Kovacs, Szabolcs,Weber, Csaba,Gati, Tamas,Meszaros, Attila,Kotschy, Andras,Novak, Zoltan
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supporting information
p. 4268 - 4271
(2014/09/30)
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- Copper-mediated perfluoroalkylation of heteroaryl bromides with (phen)CuRF
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The attachment of perfluoroalkyl groups onto organic compounds has been a major synthetic goal over the past several decades. Previously, our group reported phenanthroline-ligated perfluoroalkyl copper reagents, (phen)CuR F, which react with aryl iodides and aryl boronates to form the corresponding benzotrifluorides. Herein the perfluoroalkylation of a series of heteroaryl bromides with (phen)CuCF3 and (phen)CuCF 2CF3 is reported. The mild reaction conditions allow the process to tolerate many common functional groups. Perfluoroethylation with (phen)CuCF2CF3 occurs in somewhat higher yields than trifluoromethylation with (phen)CuCF3, creating a method to generate fluoroalkyl heteroarenes that are less accessible from trifluoroacetic acid derivatives.
- Mormino, Michael G.,Fier, Patrick S.,Hartwig, John F.
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p. 1744 - 1747
(2014/04/17)
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- Cu-catalyzed trifluoromethylation of aryl iodides with trifluoromethylzinc reagent prepared in situ from trifluoromethyl iodide
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The trifluoromethylation of aryl iodides catalyzed by copper(I) salt with trifluoromethylzinc reagent prepared in situ from trifluoromethyl iodide and Zn dust was accomplished. The catalytic reactions proceeded under mild reaction conditions, providing th
- Nakamura, Yuzo,Fujiu, Motohiro,Murase, Tatsuya,Itoh, Yoshimitsu,Serizawa, Hiroki,Aikawa, Kohsuke,Mikami, Koichi
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p. 2404 - 2409
(2014/01/06)
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- Piperazinylpyrazines with central serotoninmimetic activity.
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A series of 2-(1-piperazinyl)pyrazines was synthesized and evaluated for central serotonin-like activity. The most interesting member of the series, 6-chloro-2(1-piperazinyl)pyrazine (3a), had pharmacological properties characteristic of potent central serotoninmimetic activity and only weak peripheral serotoninmimetic action. Structural similarities between 3a and serotonin are discussed.
- Lumma et al.
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