cas 402-43-7, 4-Bromobenzotrifluoride | Articles data

Articles about 402-43-7Total 63 be found

Article title
Article abstract
Author
Journal number and time
Download

Cross-Coupling through Ag(I)/Ag(III) Redox Manifold
In ample variety of transformations, the presence of silver as an additive or co-catalyst is believed to be innocuous for the efficiency of the operating metal catalyst. Even though Ag additives are required often as coupling partners, oxidants or halide scavengers, its role as a catalytically competent species is widely neglected in cross-coupling reactions. Most likely, this is due to the erroneously assumed incapacity of Ag to undergo 2e? redox steps. Definite proof is herein provided for the required elementary steps to accomplish the oxidative trifluoromethylation of arenes through AgI/AgIII redox catalysis (i. e. CEL coupling), namely: i) easy AgI/AgIII 2e? oxidation mediated by air; ii) bpy/phen ligation to AgIII; iii) boron-to-AgIII aryl transfer; and iv) ulterior reductive elimination of benzotrifluorides from an [aryl-AgIII-CF3] fragment. More precisely, an ultimate entry and full characterization of organosilver(III) compounds [K]+[AgIII(CF3)4]? (K-1), [(bpy)AgIII(CF3)3] (2) and [(phen)AgIII(CF3)3] (3), is described. The utility of 3 in cross-coupling has been showcased unambiguously, and a large variety of arylboron compounds was trifluoromethylated via [AgIII(aryl)(CF3)3]? intermediates. This work breaks with old stereotypes and misconceptions regarding the inability of Ag to undergo cross-coupling by itself.
Demonti, Luca,Mézailles, Nicolas,Nebra, Noel,Saffon-Merceron, Nathalie
supporting information
p. 15396 - 15405
(2021/10/12)

Synthesis of ArCF2X and [18F]Ar-CF3via Cleavage of the Trifluoromethylsulfonyl Group
A versatile synthesis of ArCF2X and [18F]Ar-CF3 type compounds from readily available ArCF2SO2CF3 has been developed. Diverse nucleophiles, including weak nucleophiles such as halides (18F-, Cl-, Br-, and I-), RSH, and ROH, could react with ArCF2SO2CF3 efficiently to give the corresponding difluoromethylene products. The control experiments and the Hammett plot indicated that the reaction might proceed through a difluorocarbocation intermediate generated from the steric hindrance-assisted cleavage of the trifluoromethylsulfonyl group.
Gao, Xinyan,Gong, Kehao,Han, Junbin,Wang, Juan,Wang, Mingwei,Xu, Bo,Yang, Ren-Yin,Zeng, Xiaojun
(2021/12/17)

Preparation method of perfluoroalkylated aryl compound
The present invention provides a process for the preparation of a perfluoroalkylated aryl compound which comprises reacting an aryl compound with a perfluoroalkylsulfinate in the presence of an iron salt and hydrogen peroxide. To the method provided by the invention, perfluoroalkyl sulfinate is used as an alkylating agent, iron salt is used as a catalyst, hydrogen peroxide is used as an initiator, and the reaction time is short. The method has the characteristics of high yield, convenient operation, high safety and the like, and has wide application in the fields of drug synthesis, biological probes, fluorescent materials and the like.
-
Paragraph 0100-0103

(2021/11/14)

Base-catalyzed aryl halide isomerization enables the 4-selective substitution of 3-bromopyridines
The base-catalyzed isomerization of simple aryl halides is presented and utilized to achieve the 4-selective etherification, hydroxylation and amination of 3-bromopyridines. Mechanistic studies support isomerization of 3-bromopyridines to 4-bromopyridines proceedsviapyridyne intermediates and that 4-substitution selectivity is driven by a facile aromatic substitution reaction. Useful features of a tandem aryl halide isomerization/selective interception approach to aromatic functionalization are demonstrated. Example benefits include the use of readily available and stable 3-bromopyridines in place of less available and stable 4-halogenated congeners and the ability to converge mixtures of 3- and 5-bromopyridines to a single 4-substituted product.
Bandar, Jeffrey S.,Puleo, Thomas R.
p. 10517 - 10522
(2020/10/18)

Deoxyfluorination of acyl fluorides to trifluoromethyl compounds by FLUOLEAD/Olah's reagent under solvent-free conditions
A new protocol enabling the formation of trifluoromethyl compounds from acyl fluorides has been developed. The combination of FLUOLEAD and Olah's reagent in solvent-free conditions at 70 °C initiated the significant deoxyfluorination of the acyl fluorides and resulted in the corresponding trifluoromethyl products with high yields (up to 99%). This strategy showed a great tolerance for various acyl fluorides containing aryloyl, (heteroaryl)oyl, or aliphatic acyl moieties, providing good to excellent yields of the trifluoromethyl products. Synthetic drug-like molecules were also transformed into the corresponding trifluoromethyl compounds under the same reaction conditions. A reaction mechanism is proposed.
Liang, Yumeng,Taya, Akihito,Zhao, Zhengyu,Saito, Norimichi,Shibata, Norio
p. 3052 - 3058
(2021/01/15)

Metal- and base-free synthesis of aryl bromides from arylhydrazines
An efficient method was developed to synthesize brominated aromatic compounds from arylhydrazine hydrochlorides by using BBr3 in DMSO/CPME (cyclopentyl methyl ether) under air at 80 °C for 1 h without the use of bases or metal catalysts. In particular, this method could be carried out satisfactorily using electron-withdrawing groups to afford aryl bromides in a moderate to excellent yields.
Phuc Tran, Dat,Nomoto, Akihiro,Mita, Soichiro,Dong, Chun-ping,Kodama, Shintaro,Mizuno, Takumi,Ogawa, Akiya
supporting information

(2020/05/08)

Cathodic C-H Trifluoromethylation of Arenes and Heteroarenes Enabled by an in Situ-Generated Triflyltriethylammonium Complex
While several trifluoromethylation reactions involving the electrochemical generation of CF3 radicals via anodic oxidation have been reported, the alternative cathodic, reductive radical generation has remained elusive. Herein, the first cathodic trifluoromethylation of arenes and heteroarenes is reported. The method is based on the electrochemical reduction of an unstable triflyltriethylammonium complex generated in situ from inexpensive triflyl chloride and triethylamine, which produces CF3 radicals that are trapped by the arenes on the cathode surface.
Cantillo, David,Jud, Wolfgang,Kappe, C. Oliver,Maljuric, Snjezana
supporting information

(2019/10/08)

Aryl Sulfonium Salts for Site-Selective Late-Stage Trifluoromethylation
Incorporation of the CF3 group into arenes has found increasing importance in drug discovery. Herein, we report the first photoredox-catalyzed cross-coupling of aryl thianthrenium salts with a copper-based trifluoromethyl reagent, which enables a site-selective late-stage trifluoromethylation of arenes. The reaction proceeds with broad functional group tolerance, even for complex small molecules on gram scale. The method was further extended to produce pentafluoroethylated derivatives.
Ye, Fei,Berger, Florian,Jia, Hao,Ford, Joseph,Wortman, Alan,B?rgel, Jonas,Genicot, Christophe,Ritter, Tobias
supporting information
p. 14615 - 14619
(2019/09/17)

Mechanism of Photoredox-Initiated C-C and C-N Bond Formation by Arylation of IPrAu(I)-CF3 and IPrAu(I)-Succinimide
Herein, we report on the photoredox-initiated gold-mediated C(sp2)-CF3 and C(sp2)-N coupling reactions. By adopting gold as a platform for probing metallaphotoredox catalysis, we demonstrate that cationic gold(III) complexes are the key intermediates of the C-C and C-N coupling reactions. The high-valent gold(III) intermediates are accessed by virtue of photoredox catalysis through a radical chain process. In addition, the bond-forming step of the coupling reactions is the reductive elimination from cationic gold(III) intermediates, which is supported by isolation and crystallographic characterization of key Au(III) intermediates.
Kim, Suhong,Toste, F. Dean
p. 4308 - 4315
(2019/01/25)

Synthesis of plasmodione metabolites and 13C-enriched plasmodione as chemical tools for drug metabolism investigation
Malaria is a tropical parasitic disease threatening populations in tropical and sub-tropical areas. Resistance to antimalarial drugs has spread all over the world in the past 50 years, thus new drugs are urgently needed. Plasmodione (benzylmenadione series) has been identified as a potent antimalarial early lead drug, acting through a redox bioactivation on asexual and young sexual blood stages. To investigate its metabolism, a series of plasmodione-based tools, including a fully 13C-labelled lead drug and putative metabolites, have been designed and synthesized for drug metabolism investigation. Furthermore, with the help of UHPLC-MS/MS, two of the drug metabolites have been identified from urine of drug-treated mice.
Feng, Liwen,Lanfranchi, Don Antoine,Cotos, Leandro,Cesar-Rodo, Elena,Ehrhardt, Katharina,Goetz, Alice-Anne,Zimmermann, Herbert,Fenaille, Fran?ois,Blandin, Stephanie A.,Davioud-Charvet, Elisabeth
p. 2647 - 2665
(2018/04/27)

Visible-Light photoredox decarboxylation of perfluoroarene iodine(III) Trifluoroacetates for C-H trifluoromethylation of (Hetero)arenes
A scalable and operationally simple decarboxylative trifluoromethylation of (hetero)arenes with easily accessible C6F5I(OCOCF3)2 under photoredox catalysis has been developed. This method is tolerant of various (hetero)arenes and functional groups. Notably, C6F5I is recycled from the decarboxylation reaction and further used for the preparation of C6F5I(OCOCF3)2. The combination of photoredox catalysis and hypervalent iodine reagent provides a practical approach for the application of trifluoroacetic acid in trifluoromethylation reactions.
Yang, Bin,Yu, Donghai,Xu, Xiu-Hua,Qing, Feng-Ling
p. 2839 - 2843
(2018/04/14)

A general electrochemical strategy for the Sandmeyer reaction
Herein we report a general electrochemical strategy for the Sandmeyer reaction. Using electricity as the driving force, this protocol employs a simple and inexpensive halogen source, such as NBS, CBrCl3, CH2I2, CCl4, LiCl and NaBr for the halogenation of aryl diazonium salts. In addition, we found that these electrochemical reactions could be performed using anilines as the starting material in a one-pot fashion. Furthermore, the practicality of this process was demonstrated in the multigram scale synthesis of aryl halides using highly inexpensive graphite as the electrode. A series of detailed mechanism studies have been performed, including radical clock and radical scavenger study, cyclic voltammetry analysis and in situ electron paramagnetic resonance (EPR) analysis.
Liu, Qianyi,Sun, Beiqi,Liu, Zheng,Kao, Yi,Dong, Bo-Wei,Jiang, Shang-Da,Li, Feng,Liu, Guoquan,Yang, Yang,Mo, Fanyang
p. 8731 - 8737
(2018/12/10)

One-Pot, Metal-Free Conversion of Anilines to Aryl Bromides and Iodides
A metal-free synthesis of aryl bromides and iodides from anilines via halogen abstraction from bromotrichloromethane and diiodomethane is described. This one-pot reaction affords aryl halides from the corresponding anilines in moderate to excellent yields without isolation of diazonium salts. The transformation has short reaction times, a simple workup, and insensitivity to moisture and air and avoids excess halogenation. DFT calculations support a SRN1 mechanism. This method represents a convenient alternative to the classic Sandmeyer reaction.
Leas, Derek A.,Dong, Yuxiang,Vennerstrom, Jonathan L.,Stack, Douglas E.
supporting information
p. 2518 - 2521
(2017/05/24)

Synthesis of trifluoromethyl moieties by late-stage copper (I) mediated nucleophilic fluorination
The nucleophilic fluorination of bromodifluoromethyl derivatives mediated by the complex (PPh3)3CuF is described. Under the reaction conditions, different trifluoroacetates, trifluoroketones, trifluoroarenes and trifluoroacetamides were obtained in good yields.
Bermejo Góme, Antonio,González, Miguel A. Cortés,Lübcke, Marvin,Johansson, Magnus J.,Schou, Magnus,Szabó, Kálmán J.
p. 51 - 57
(2017/01/12)

Copper-Promoted Conversion of Aromatic Amines into Trifluoromethylated Arenes: One-Pot Sandmeyer Trifluoromethylation
A simple copper-promoted one-pot Sandmeyer trifluoromethylation of aromatic amines with Langlois’ reagent has been demonstrated. The reaction is performed in mild reaction conditions under an air atmosphere with good substrate scope and functional group compatibility. It provides an alternative and straightforward synthetic approach to access a variety of trifluoromethylated arenes.
Hong, Jianquan,Wang, Guifu,Huo, Lianguang,Zheng, Changge
supporting information
p. 1761 - 1767
(2017/09/06)

NOVEL TRIFLUOROMETHYLATION AGENT, AND METHOD FOR PRODUCING TRIFLUOROMETHYL GROUP-CONTAINING COMPOUND USING THE SAME
PROBLEM TO BE SOLVED: To provide a trifluoromethylation agent useful as medical and agrochemical intermediates and electronic material intermediates, and a method for producing a trifluoromethyl group-containing compound using the same. SOLUTION: The present invention provides a method for producing a trifluoromethyl group-containing compound by making trifluoromethyl group-containing borate salt represented by formula (1) react with aromatic iodide, in the presence of a copper salt catalyst and a ligand (R1 is methyl, ethyl or C3-10 straight, branched, or cyclic alkyl). SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
-
Paragraph 0052

(2017/07/25)

Nucleophile promoted gold redox catalysis with diazonium salts: C-Br, C-S and C-P bond formation through catalytic Sandmeyer coupling
Gold-catalyzed C-heteroatom (C-X) coupling reactions are evaluated without using sacrificial oxidants. Vital to the success of this methodology is the nucleophile-assisted activation of aryldiazonium salts, which could be an effective oxidant for converting Au(i) to Au(iii) even without the addition of an assisting ligand or photocatalyst. By accelerating the reaction kinetics to outcompete C-C homo-coupling or diazonium dediazoniation, gold-catalyzed Sandmeyer reactions were achieved with different nucleophiles, forming C-Br, C-S and C-P bonds in high yields and selectivities.
Peng, Haihui,Cai, Rong,Xu, Chang,Chen, Hao,Shi, Xiaodong
p. 6190 - 6196
(2016/09/03)

Trifluoromethylation of (hetero)aryl iodides and bromides with copper(i) chlorodifluoroacetate complexes
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
p. 75465 - 75469
(2016/08/24)

Copper-catalysed synthesis of trifluoromethyl(hetero)arenes from di(hetero)aryl-λ3-iodanes
An efficient synthesis of trifluoromethylated (hetero)arenes has been achieved through the regioselective copper-catalyzed trifluoromethylation of di(hetero)aryl-λ3-iodanes, employing readily available trifluoromethyltrimethylsilane. The reaction works well for both symmetrical and unsymmetrical di(hetero)aryl-λ3-iodanes with good regioselectivity and also tolerates diverse functional groups such as bromo, iodo, cyano, nitro, ester, ketone and enolizable ketone.
Pandey, Vinay Kumar,Anbarasan, Pazhamalai
p. 18525 - 18529
(2016/02/27)

TCDA: Practical Synthesis and Application in the Trifluoromethylation of Arenes and Heteroarenes
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
p. 836 - 839
(2016/05/19)

Copper-mediated trifluoromethylation of diaryliodonium salts with TMSCF3 at room temperature
A convenient method for the preparation of trifluoromethylated arenes from the reaction of diaryliodonium salts with TMSCF3 in the presence of CuBF4·(MeCN)4 and KF at room temperature within 25 min was developed. This reaction provides a valuable complement to the previously established trifluoromethylation methods.
Yang, Jing-Yun,Xu, Xiu-Hua,Qing, Feng-Ling
p. 175 - 180
(2015/10/20)

Oxidation of Ni(II) to Ni(IV) with Aryl Electrophiles Enables Ni-Mediated Aryl-CF3 Coupling
This communication describes the synthesis and reactivity of NiIV(aryl)(CF3)2 complexes supported by trispyrazolylborate and 4,4′-di-tert-butylbipyridine ligands. We demonstrate that isolable NiIV complexes can be accessed under mild conditions via the oxidation of NiII precursors with S-(trifluoromethyl)dibenzothiophenium triflate as well as with diaryliodonium and aryl diazonium reagents. The NiIV intermediates undergo high yielding aryl-CF3 bond-forming reductive elimination. These studies support the potential viability of NiIV intermediates in nickel-catalyzed coupling reactions involving diaryliodonium and aryldiazonium electrophiles.
Bour, James R.,Camasso, Nicole M.,Sanford, Melanie S.
supporting information
p. 8034 - 8037
(2015/07/08)

Copper-Promoted Trifluoromethanesulfonylation and Trifluoromethylation of Arenediazonium Tetrafluoroborates with NaSO2CF3
A tunable chemoselective trifluoromethanesulfonylation and trifluoromethylation of arenediazonium tetrafluoroborates with Langlois' reagent (NaSO2CF3) was developed. The Cu2O-catalyzed reaction in DMSO gave aryl trifluoromethanesulfones as the major products. On the other hand, the trifluoromethylated arenes were produced in the presence of oxidant tert-butyl hydroperoxide, CuBF4(MeCN)4, and 2,2′;6′,2 terpyridine (tpy). Both of these transformations proceed under mild conditions and tolerate functional groups.
Zhang, Ke,Xu, Xiu-Hua,Qing, Feng-Ling
p. 7658 - 7665
(2015/08/18)

New Reagent for Highly Efficient Synthesis of Trifluoromethyl-Substituted Arenes and Heteroarenes
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
supporting information
p. 2086 - 2089
(2015/05/13)

Introducing a new radical trifluoromethylation reagent
Perfluoro-3-ethyl-2,4-dimethyl-3-pentyl radical (PPFR) is a persistent radical stable at room temperature, but easily decomposes at 90 °C to produce a CF3 radical which is able to react with a variety of aromatic compounds to afford the corresponding trifluoromethyl derivatives, usually as mixtures of regioisomers in good to excellent overall yields.
Sato, Azusa,Han, Jianlin,Ono, Taizo,Wzorek, Alicja,Ace?a, José Luis,Soloshonok, Vadim A.
supporting information
p. 5967 - 5970
(2015/03/30)

Efficient copper-catalyzed trifluoromethylation of aromatic and heteroaromatic iodides: The beneficial anchoring effect of borates
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
supporting information
p. 4268 - 4271
(2014/09/30)

Trifluoromethylation of arenediazonium salts with fluoroform-derived CuCF3 in aqueous media
A new protocol has been developed for trifluoromethylation of arenediazonium salts with moisture-sensitive CuCF3 (from fluoroform) in aqueous media. The reaction is governed by a radical mechanism, tolerates a broad variety of functional groups, and is applicable to the synthesis of complex, polyfunctionalized molecules. This journal is the Partner Organisations 2014.
Lishchynskyi, Anton,Berthon, Guillaume,Grushin, Vladimir V.
supporting information
p. 10237 - 10240
(2014/08/18)

Copper-mediated trifluoromethylation of aryl-, heteroaryl-, and vinyltrifluoroborates with Langlois' reagent
An effortless and realistic procedure for the copper-mediated trifluoromethylation of aryl-, heteroaryl- and vinyltrifluoroborates with CF3 radicals generated from NaSO2CF3 and tert-butyl hydroperoxide (TBHP) is presented. The developed method produces trifluoromethyl arenes and -alkenes in good to excellent yields and a wide range of electronically and structurally diverse substrates are tolerated.
Dubbaka, Srinivas Reddy,Salla, Manohar,Bolisetti, Raghu,Nizalapur, Shashidhar
p. 6496 - 6499
(2014/02/14)

Conversion of aromatic amino into trifluoromethyl groups through a Sandmeyer-type transformation
A novel strategy for aromatic trifluoromethylation by converting amino into trifluoromethyl groups via a Sandmeyer-type reaction is reported. The transformation involves diazotization of the aromatic amines with tert-butyl nitrite and hydrochloric acid to form aryldiazonium chlorides, followed by trifluoromethylation with trifluoromethylsilver at low temperature. Various readily available aromatic amines are smoothly converted under mild conditions. Georg Thieme Verlag Stuttgart. New York.
Wang, Xi,Xu, Yan,Zhou, Yujing,Zhang, Yan,Wang, Jianbo
supporting information
p. 2143 - 2148
(2014/08/18)

Trifluoromethylation of aryl and heteroaryl halides with fluoroform-derived CuCF3: Scope, limitations, and mechanistic features
Fluoroform-derived CuCF3 recently discovered in our group exhibits remarkably high reactivity toward aryl and heteroaryl halides, performing best in the absence of extra ligands. A broad variety of iodoarenes undergo smooth trifluoromethylation with the ligandless CuCF3 at 23-50 C to give the corresponding benzotrifluorides in nearly quantitative yield. A number of much less reactive aromatic bromides also have been trifluoromethylated, including pyridine, pyrimidine, pyrazine, and thiazole derivatives as well as aryl bromides bearing electron-withdrawing groups and/or ortho substituents. Only the most electrophilic chloroarenes can be trifluoromethylated, e.g., 2-chloronicotinic acid. Exceptionally high chemoselectivity of the reactions (no side-formation of arenes, biaryls, and C2F5 derivatives) has allowed for the isolation of a large number of trifluoromethylated products in high yield on a gram scale (up to 20 mmol). The CuCF3 reagent is destabilized by CuX coproduced in the reaction, the magnitude of the effect paralleling the Lewis acidity of CuX: CuCl > CuBr > CuI. While SNAr and SRN1 mechanisms are not operational, there is a well-pronounced ortho effect, i.e., the enhanced reactivity of ortho-substituted aryl halides 2-RC6H4X toward CuCF3. Intriguingly, this ortho-effect is observed for R = NO2, COOH, CHO, COOEt, COCH3, OCH3, and even CH3, but not for R = CN. The fluoroform-derived CuCF3 reagent and its reactions with haloarenes provide an unmatched combination of reactivity, selectivity, and low cost.
Lishchynskyi, Anton,Novikov, Maxim A.,Martin, Eddy,Escudero-Adan, Eduardo C.,Novak, Petr,Grushin, Vladimir V.
p. 11126 - 11146
(2013/12/04)

Silver-mediated trifluoromethylation of aryldiazonium salts: Conversion of amino group into trifluoromethyl group
A novel strategy for aromatic trifluoromethylation by converting aromatic amino group into CF3 group is reported herein. This method, which can be considered as trifluoromethylation variation of the classic Sandmeyer reaction, uses readily available aromatic amines as starting materials and is performed under mild conditions.
Wang, Xi,Xu, Yan,Mo, Fanyang,Ji, Guojing,Qiu, Di,Feng, Jiajie,Ye, Yuxuan,Zhang, Songnan,Zhang, Yan,Wang, Jianbo
supporting information
p. 10330 - 10333
(2013/08/23)

Catalytic decarboxylative fluorination for the synthesis of Tri- and difluoromethyl arenes
Treatment of readily available α,α-difluoro- and α-fluoroarylacetic acids with Selectfluor under Ag(I) catalysis led to decarboxylative fluorination. This operationally simple reaction gave access to tri- and difluoromethylarenes applying a late-stage fluorination strategy. Translation to [18F]labeling is demonstrated using [ 18F]Selectfluor bis(triflate), a reagent affording [ 18F]tri- and [18F]difluoromethylarenes not within reach with [18F]F2.
Mizuta, Satoshi,Stenhagen, Ida S.R.,O'Duill, Miriam,Wolstenhulme, Jamie,Kirjavainen, Anna K.,Forsback, Sarita J.,Tredwell, Matthew,Sandford, Graham,Moore, Peter R.,Huiban, Mickael,Luthra, Sajinder K.,Passchier, Jan,Solin, Olof,Gouverneur, Véronique
supporting information
p. 2648 - 2651
(2013/07/11)

Copper-catalyzed trifluoromethylation of aryl- and vinylboronic acids with generation of CF3-radicals
The selective trifluoromethylation of aryl- and vinylboronic acids proceeds smoothly with CF3SO2Na (Langlois reagent) in the presence of copper catalysts and t-BuOOH. Therefore, the method relies both on transition metal catalysis an
Li, Yang,Wu, Lipeng,Neumann, Helfried,Beller, Matthias
supporting information
p. 2628 - 2630
(2013/04/23)

Copper-catalysed process for the production of substituted or unsubstituted trifluormethylated aryl and heteroaryl compounds
The present invention relates to a process for the production of triffluoromethylated unsubstituted or substituted aryl or heteroaryl compounds which comprises reacting an unsubstituted or substituted aryl or heteroaryl halide with a trifluoroacetate of formula (I) or (II), wherein R1 is hydrogen or a C1-C5 alkyl group and M an alkali metal or an ammonium ion, in the presence of a copper salt as catalyst and an anorganic halogenide salt or a trifluoroacetacid salt as activator compound.
-
Page/Page column 5; 8

(2012/05/20)

FLUOROALKYLATION METHODS AND REAGENTS
A method of forming a fluorinated molecular entity includes reacting in a reaction mixture an aromatic halide, copper, a fluoroalkyl group, and a ligand. The aromatic halide includes an aromatic group and a halogen substituent bonded to the aromatic group. The ligand includes at least one group-V donor selected from phosphorus and an amine. The overall molar ratio of copper to aromatic halide in the reaction mixture is from 0.2 to 3. The method further includes forming a fluoroalkylarene including the aromatic group and the fluoroalkyl group bonded to the aromatic group. A composition, which may be used in the method, consists essentially of copper, the fluoroalkyl group, and the ligand, where the molar ratio of copper to the fluoroalkyl group is approximately 1.
-
Page/Page column title page; 6; 28

(2012/03/11)

Silver catalyzed bromination of aromatics with N-bromosuccinimide
A heterogeneous silver catalyst was prepared and applied efficiently for the selective bromination of aromatics with NBS. The silver nanoparticles combined with the acidic support HMB can activate both the aromatic ring and NBS, and the synergistic effects between the silver nanoparticles and the HMB highly enhanced the efficiency of the bromination reaction.
Zhang, Rui,Huang, Lei,Zhang, Yanfang,Chen, Xiaorong,Xing, Weihong,Huang, Jun
experimental part
p. 378 - 383
(2012/06/18)

A general strategy for the perfluoroalkylation of arenes and arylbromides by using arylboronate esters and [(phen)CuRF]
A versatile method for the synthesis of aryl perfluoroalkanes from arenes and aryl bromides is described. Substituted arenes or aryl bromides are converted in situ to an aryl boronate ester that readily undergoes perfluoroalkylation in air with [(phen)CuRF]. A broad range of aryl bromide substrates were perfluoroalkylated in good yield for the first time. [(phen)CuCF3] is now commercially available and has been prepared on 20g scale. Copyright
Litvinas, Nichole D.,Fier, Patrick S.,Hartwig, John F.
supporting information; scheme or table
p. 536 - 539
(2012/02/16)

Copper-catalyzed oxidative trifluoromethylation of terminal alkynes and aryl boronic acids using (trifluoromethyl)trimethylsilane
Trifluoromethylated acetylenes and arenes are widely applicable in the synthesis of pharmaceuticals and agrochemicals. In 2010, our group has reported the copper-mediated oxidative trifluomethylation of terminal alkynes and aryl boronic acids. This method allows a wide range of functional group tolerant trifluoromethylated acetylenes and arenes to be easily prepared. After the preliminary mechanistic studies of the oxidative trifluoromethylation of terminal alkyne, an efficient copper-catalyzed oxidative trifluoromethylation of terminal alkynes and aryl boronic acids has been developed. The catalytic protocol is successfully achieved by adding both the substrate and a portion of CF3TMS slowly using a syringe pump to the reaction mixture.
Jiang, Xueliang,Chu, Lingling,Qing, Feng-Ling
experimental part
p. 1251 - 1257
(2012/03/22)

Halodeboronation of organotrifluoroborates using tetrabutylammonium tribromide or cesium triiodide
Halodeboronation of organotrifluoroborates using commercially available tetrabutylammonium tribromide (TBATB) or cesium triiodide in aqueous medium is reported. The mild, transition metal-free method has proven to be tolerant of a wide range of functional groups. High regio- and chemoselectivity are observed. Two synthetic routes to (Z)-dibromoalkenes from alkynes, through stereodefined (Z)-2-bromoalkenyltrifluoroborates and (Z)-1,2-bis(boryl) alkenyltrifluoroborates, have been developed using the TBATB mediated bromodeboronation as the key step.
Yao, Min-Liang,Kabalka, George W.,Blevins, David W.,Reddy, Marepally Srinivasa,Yong, Li
experimental part
p. 3738 - 3743
(2012/06/30)

Copper-catalyzed aromatic trifluoromethylation via group transfer from fluoral derivatives
Starting from a readily available fluoral derivative, catalytic aromatic trifluoromethylation has been successfully achieved. A small amount of copper(I) iodide-phenanthroline complex catalyzed the cross-coupling reactions of aryl/heteroaryl iodides with the O-silylated hemiaminal of fluoral (trifluoroacetaldehyde) to provide trifluoromethylated arenes in moderate to high yields.
Kondo, Hideaki,Oishi, Masahiro,Fujikawa, Kenichi,Amii, Hideki
supporting information; experimental part
p. 1247 - 1252
(2011/07/08)

Highly regioselective amination of unactivated alkanes by hypervalent sulfonylimino-δ3-bromane
Amination of alkanes has generally required metal catalysts and/or high temperatures. Here we report that simple exposure of a broad range of alkanes to N-triflylimino-δ3-bromane 1 at ambient temperature results in C-H insertion of the nitrogen functionality to afford triflyl-substituted amines in moderate to high yields. Marked selectivity for tertiary over secondary C-H bonds was observed; primary (methyl) C-H bonds were inert. Addition of hexafluoroisopropanol to inhibit decomposition of 1 dramatically improved the C-H amination efficiencies. Second-order kinetics, activation parameters (negative activation entropy), deuterium isotope effects, and theoretical calculations suggest a concerted asynchronous bimolecular transition state for the metal-free C-H amination event.
Ochiai, Masahito,Miyamoto, Kazunori,Kaneaki, Takao,Hayashi, Satoko,Nakanishi, Waro
scheme or table
p. 448 - 451
(2011/10/31)

A broadly applicable copper reagent for trifluoromethylations and perfluoroalkylations of aryl iodides and bromides
(Chemical Presented) Well compatible: The trifluoromethylations and perfluoroalkylations of aryl iodides and some aryl bromides with trifluoromethyl and perfluoroalkylcopper(I) phenanthroline complexes occur with broad scope at 25-50 8C (see scheme). The trifluoromethyl complex is prepared from inexpensive reagents and can be used in situ or isolated. The reactions tolerate a range of substituents and also occur with heteroaromatic systems.
Morimoto, Hiroyuki,Tsubogo, Tetsu,Litvinas, Nichole D.,Hartwig, John F.
supporting information; experimental part
p. 3793 - 3798
(2011/05/15)

Weakly nucleophilic conjugate bases of superacids as powerful nucleophiles in vinylic bimolecular nucleophilic substitutions of simple β- alkylvinyl(aryl)-λ3-bromanes
We report herein, for the first time, the stereoselective synthesis of simple (E)-β-alkylvinyl(aryl)-λ3-bromanes via a boron-λ3-bromane exchange reaction and their unique bimolecular nucleophilic substitutions at the vinylic ipso carbon atom under mild conditions. Interestingly, even weakly nucleophilic anions such as conjugate bases of superacids (HBF4, TfOH, Tf2CH 2, Tf3CH, Tf2NH, etc.) function as nucleophiles toward the vinyl-λ3-bromanes. For instance, the vinylic SN2 reaction of (E)-vinyl-λ3-bromanes with potassium bis(triflyl)methanide stereoselectively produced (Z)-vinyloxy oxosulfonium ylides with exclusive inversion of configuration via oxygen attack, while that with potassium bis(triflyl)imide afforded predominantly (Z)-vinyloxysulfoximines. In marked contrast, (E)-β-alkylvinyl- λ3-iodanes do not undergo the vinylic SN2 reaction with these conjugate bases of superacids. The differences between the nucleofugalities of aryl-λ3-iodanyl and aryl- λ3-bromanyl groups (the latter being greater) probably play a pivotal role in these unique reactions.
Ochiai, Masahito,Okubo, Takuji,Miyamoto, Kazunori
p. 3342 - 3344
(2011/05/04)

Copper-catalyzed trifluoromethylation of aryl iodides with potassium (trifluoromethyl)trimethoxyborate
Potassium (trifluoromethyl)trimethoxyborate is introduced as a new source of CF3 nucleophiles in copper-catalyzed trifluoromethylation reactions. The crystalline salt is stable on storage, easy to handle, and can be obtained in near-quantitative yields simply by mixing B(OMe)3, CF3SiMe3, and KF. The trifluoromethylation reagent allows the conversion of various aryl iodides into the corresponding benzotrifluorides in high yields under mild, base-free conditions in the presence of catalytic quantities of a CuI/1,10-phenanthroline complex.
Knauber, Thomas,Arikan, Fatih,Roeschenthaler, Gerd-Volker,Goossen, Lukas J.
experimental part
p. 2689 - 2697
(2011/04/15)

Copper-mediated oxidative trifluoromethylation of boronic acids
A copper-mediated oxidative cross-coupling of aryl- and alkenylboronic acids with (trifluoromethyl)trimethylsilane (Me3SiCF3) under mild conditions has been developed. This method allows a wide range of functional group tolerant trifluoromethylated arenes and alkenes to be easily prepared. This oxidative trifluoromethylation has the potential to introduce trifluoromethyl groups into advanced, highly functionalized organic molecules.
Chu, Lingling,Qing, Feng-Ling
supporting information; experimental part
p. 5060 - 5063
(2010/12/29)

New types of asymmetrical bromonium salts [RF(R F′)Br]Y where RF and/or RF′ represent perfluorinated aryl, alkenyl, and alkynyl groups
A series of previously unknown asymmetrical fluorinated bis(aryl)bromonium, alkenyl(aryl)bromonium, and alkynyl(aryl)bromonium salts was prepared by reactions of C6F5BrF2 or 4-CF3C 6H4BrF2 with aryl group transfer reagents Ar′SiF3 (Ar′ = C6F5, 4-FC 6H4, C6H5) or perfluoroorganyl group transfer reagents RF′BF2 (RF = C 6F5, trans-CF3CFCF, C3F 7C≡C) preferentially in weakly coordinating solvents (CCl 3F, CCl2FCClF2, CH2Cl2, CF3CH2CHF2 (PFP), CF3CH 2CF2CH3 (PFB)). The presence of the base MeCN and the influence of the adducts RF′BF2·NCMe (RF = C6F5, CF3C≡C) on reactions aside to bromonium salt formation are discussed. Reactions of C 6F5BrF2 with AlkF′BF 2 in PFP gave mainly C6F5Br and Alk F′F (AlkF′ = C6F13, C6F13CH2CH2), presumably, deriving from the unstable salts [C6F5(AlkF′)Br]Y (Y = [AlkF′BF3]-). Prototypical reactivities of selected bromonium salts were investigated with the nucleophile I-and the electrophile H+. [4-CF3C 6H4(C6F5)Br][BF4] showed the conversion into 4-CF3C6H4Br and C 6F5I when reacted with [Bu4N]I in MeCN. Perfluoroalkynylbromonium salts [CnF2n+1C≡C(R F)Br][BF4] slowly added HF when dissolved in aHF and formed [Z-CnF2n+1CFCH(RF)Br][BF4].
Frohn, Hermann-Josef,Giesen, Matthias,Bardin, Vadim V.
experimental part
p. 969 - 974
(2010/12/19)

From carboxylic acids to the trifluoromethyl group using BrF3
Organic trifluoromethyl derivatives were made from aromatic and aliphatic carboxylic acids by transforming them first into the corresponding dithioesters followed by reaction with bromine trifluoride under mild conditions (0 °C, 2 min).
Cohen, Or,Mishani, Eyal,Rozen, Shlomo
experimental part
p. 3579 - 3582
(2010/07/04)

Chemoselective bromodeboronation of organotrifluoroborates using tetrabutylammonium tribromide: Application in (Z)-dibromoalkene syntheses
(Chemical Equation Presented) Tetrabutylammonlum trlbromlde (TBATB) has been found to be a unique bromodeboronatlon reagent for organotrlf luoroborates. When compared to previously reported bromodeboronatlon methods, the mild and metal-free reaction conditions tolerate a wider range of functional groups. High reglo- and chemoselectlvlty are observed In the presence of both unsaturated carbon-carbon bonds and aldehyde functional groups. An efficient synthetic route to (Z)-dlbromoalkenes from terminal alkynes has been developed using the TBATB-medlated bromodeboronatlon as a key step.
Yao, Min-Liang,Reddy, Marepally Srinivasa,Li, Yong,Walfish, Ingrid,Blevins, David W.,Kabalka, George W.
supporting information; experimental part
p. 700 - 703
(2010/04/02)

Oxidation of benzyl alcohols with difluoro(aryl)-λ3-bromane: formation of benzyl fluoromethyl ethers via oxidative rearrangement
Oxidative rearrangement of benzyl alcohols with difluoro(p-trifluoromethylphenyl)-λ3-bromane (5 × 10-2 M) in chloroform at room temperature afforded aryl fluoromethyl ethers selectively in good yields, probably via 1,2-shift of aryl groups from benzylic carbon to oxygen atoms.
Ochiai, Masahito,Yoshimura, Akira,Miyamoto, Kazunori
body text
p. 4792 - 4795
(2011/03/18)

Facile generation of a strained cyclic vinyl cation by thermal solvolysis of cyclopent-1-enyl-λ3-bromanes
Last of the cyclic vinyl cations: The simple solvolysis of cyclopent-1 -enyl-13-bromane efficiently generates the highly strained cyclopent-1 -enyl cation at room temperature (see scheme). The very high nucleofugality of the aryl-13-bromanyl groups are re
Miyamoto, Kazunori,Shiro, Motoo,Ochiai, Masahito
supporting information; experimental part
p. 8931 - 8934
(2010/02/28)