- Aryl Ether Syntheses via Aromatic Substitution Proceeding under Mild Conditions
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In this study, mild conditions for aromatic substitutions during the syntheses of aryl ethers were developed. In the reaction conditions, the choices of solvent, base, and the sequence for the addition of the reagents proved important. A wide variety of alcohols were used directly as nucleophiles and smoothly reacted with aryl chlorides that possessed either a nitro or a cyano group at either the ortho- or para-position. Controlled experiments we performed suggested that the reaction underwent a charge-transfer process mediated by a combination of DMF and tert-BuOK.
- Ando, Shin,Tsuzaki, Marina,Ishizuka, Tadao
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p. 11181 - 11189
(2020/10/12)
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- Practical heterogeneous photoredox/nickel dual catalysis for C-N and C-O coupling reactions
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Efficient C-N and C-O coupling reactions of aryl halides with amines and alcohols have been developed by using the strategy of heterogeneous visible light photoredox and nickel dual catalysis. Obviously, the joint use of inexpensive and bench-stable CdS and nickel salts, together with mild reaction conditions, makes these two transformations attractive for the synthetic community. This heterogeneous dual catalysis system also proved to be successful in the ligand-free catalytic hydroxylation of aryl bromide with water as a nucleophile. The practicality of this protocol is further emphasized by the scaled-up reaction and the reusability of heterogeneous photocatalysts.
- Liu, Yi-Yin,Liang, Dong,Lu, Liang-Qiu,Xiao, Wen-Jing
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supporting information
p. 4853 - 4856
(2019/05/02)
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- Transition-Metal-Free Aryl-Heteroatom Bond Formation via C-S Bond Cleavage
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Aryl-heteroatom bonds (C-Het) are almost ubiquitously present in chemical molecules. However, methods for diverse C-Het bond formations from a simple substrate are limited. Herein, we report a convenient and efficient C-S bond transformation of aryl sulfoniums to various C-Het bonds (C-O, C-S, C-Sn, C-Si, C-Se) in the absence of any transition-metal catalyst. These reactions proceeded in mild conditions with a wide substrate scope.
- Zhao, Jian-Nan,Kayumov, Muzaffar,Wang, Dong-Yu,Zhang, Ao
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p. 7303 - 7306
(2019/10/02)
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- From Anilines to Aryl Ethers: A Facile, Efficient, and Versatile Synthetic Method Employing Mild Conditions
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We have developed a simple and direct method for the synthesis of aryl ethers by reacting alcohols/phenols (ROH) with aryl ammonium salts (ArNMe3+), which are readily prepared from anilines (ArNR′2, R′=H or Me). This reaction proceeds smoothly and rapidly (within a few hours) at room temperature in the presence of a commercially available base, such as KOtBu or KHMDS, and has a broad substrate scope with respect to both ROH and ArNR′2. It is scalable and compatible with a wide range of functional groups.
- Wang, Dong-Yu,Yang, Ze-Kun,Wang, Chao,Zhang, Ao,Uchiyama, Masanobu
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p. 3641 - 3645
(2018/03/13)
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- Copper-catalyzed oxidative trifluoroethoxylation of aryl boronic acids with CF3CH2OH
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A mild and efficient copper-catalyzed oxidative trifluoroethoxylation of aryl and heteroaryl boronic acids with CF3CH2OH has been developed. This protocol tolerates a range of functional groups, allowing access to a variety of aryl and heteroaryl trifluoroethyl ethers.
- Zhang, Ke,Xu, Xiu-Hua,Qing, Feng-Ling
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- Palladium-Catalyzed 2,2,2-Trifluoroethoxylation of Aromatic and Heteroaromatic Chlorides Utilizing Borate Salt and the Synthesis of a Trifluoro Analogue of Sildenafil
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A simple and convenient method was developed for the introduction of a 2,2,2-trifluoroethoxy group to various aromatic and heteroaromatic systems. The novel process utilizes aromatic chlorides as substrates, and tetrakis(2,2,2-trifluoroethoxy) borate salt as an inexpensive and readily available fluoroalkoxy source in a palladium-catalyzed cross-coupling reaction. The power of the developed methodology was demonstrated in the synthesis of a fluorous derivative of Sildenafil.
- Peth?, Bálint,Zwillinger, Márton,Csenki, János T.,Káncz, Anna E.,Krámos, Balázs,Müller, Judit,Balogh, Gy?rgy T.,Novák, Zoltán
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supporting information
p. 15628 - 15632
(2017/10/20)
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- Method for preparing aryl trifluoroethoxyl ether
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The invention relates to a method for preparing aryl trifluoroethoxyl ether. The method includes the steps that aryl boron compounds and trifluoroethanol are added to organic solvent, a copper salt catalyst, a ligand and an oxidizing agent are added, a reaction is conducted in a stirring mode for 1-40 hours at the temperature of 0-60 DEG C, filtering is conducted, column chromatography isolation is conducted, and the aryl trifluoroethoxyl ether is obtained. The method is simple in operation, raw materials are easy to obtain, the reaction condition is mild, the substrate universality is wide, the environmental friendliness is achieved, and the method is applicable to industrial application.
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Paragraph 0057; 0058; 0059; 0060;
(2016/10/07)
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- A general, mild and efficient palladium-catalyzed 2,2,2-trifluoroethoxylation of activated aryl bromides and bromo-chalcones: Bromo-chalcones a new coupling partner in cross-coupling reaction
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An efficient protocol for Pd-catalyzed 2,2,2-trifluoroethoxylation of activated aryl bromides and bromo-chalcones has been developed. We unveil a fascinating insight into the Pd-catalyzed C-O cross-coupling reaction. Pd/tBuXPhos (L1) ligand system facilitates the C-O cross-coupling reaction between 2,2,2-trifluoroethanol and activated aryl bromides at both higher (115 °C) and lower temperatures (40 °C). Unprecedentedly, this catalyst system facilitates the C-O cross-coupling reaction in short span of reaction times, generally 5-25 min (at 115 °C). The structurally simple analogue of tBuXPhos ligand so called JohnPhos (L2) ligand is also facilitated the C-O bond formation with activated aryl bromides and bromo-chalcones. Interestingly, under the optimal conditions (L1), methanol is also coupled rapidly with activated aryl bromides. These catalyst systems (L1 and L2) fail to couple electron rich aryl bromides with 2,2,2-trifluoroethanol, thus these catalyst systems allow the reductive elimination through an electronic pathway of reductive elimination. The unusual reactivity of 2,2,2-trifluoroethanol in Pd-catalyzed C-O cross-coupling reaction makes that the chemistry of fluorinated molecules is unique than that of non-fluorinated analogues. The bromo-chalcones can be used as a new coupling partner in the cross-coupling reaction.
- Rangarajan,Devi, Kavita,Ayushee,Prasad, Ashok K.,Pal Singh, Rishi
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p. 8307 - 8314
(2015/10/05)
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- Well-defined copper(I) fluoroalkoxide complexes for trifluoroethoxylation of aryl and heteroaryl bromides
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Copper(I) fluoroalkoxide complexes bearing dinitrogen ligands were synthesized and the structure and reactivity of the complexes toward trifluoroethoxylation, pentafluoropropoxylation, and tetrafluoropropoxylation of aryl and heteroaryl bromides were investigated. Efficiency drive: A series of copper(I) fluoroalkoxide complexes bearing N,N ligands have been prepared and structurally characterized. These well-defined complexes serve as efficient reagents for the fluoroalkoxylation of aryl and heteroaryl bromides to produce a wide range of trifluoroethyl, pentafluoropropyl, and tetrafluoropropyl (hetero)aryl ethers in good to excellent yields.
- Huang, Ronglu,Huang, Yangjie,Lin, Xiaoxi,Rong, Mingguang,Weng, Zhiqiang
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supporting information
p. 5736 - 5739
(2015/05/19)
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- Transition-Metal-Mediated Synthesis of Trifluoroethyl Aryl Ethers
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A series of well-defined copper(I) fluoroalkoxide complexes, [(phen)2Cu][OCH2RF], have been shown to undergo trifluoroethoxylation, pentafluoropropoxylation, and tetrafluoropropoxylation with aryl and heteroaryl bromides to generate the corresponding trifluoroethyl, pentafluoropropyl, and tetrafluoropropyl (hetero)aryl ethers in good to excellent yields. The reaction tolerates a variety of functional groups and demonstrates efficient scalability and practicality.
- Huang, Yangjie,Huang, Ronglu,Weng, Zhiqiang
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p. 2327 - 2331
(2015/10/19)
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- BrettPhos ligand supported palladium-catalyzed C-O bond formation through an electronic pathway of reductive elimination: Fluoroalkoxylation of activated aryl halides
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We report an unprecedented BrettPhos ligand supported Pd-catalyzed C-O bond-forming reaction of activated aryl halides with primary fluoroalkyl alcohols. We demonstrate that the Phosphine ligand (BrettPhos) possesses the property of altering the mechanistic pathway of reductive elimination from nucleophile to nucleophile. The Pd/BrettPhos catalyst system facilitates the reductive elimination of the oxygen nucleophile through an electronic pathway.
- Rangarajan,Singh, Rajendra,Brahma, Raju,Devi, Kavita,Singh, Rishi Pal,Singh,Prasad, Ashok K.
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supporting information
p. 14218 - 14225
(2015/01/09)
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- A simple, rapid procedure for nucleophilic radiosynthesis of aliphatic [18F]trifluoromethyl groups
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A procedure for the radiosynthesis of aliphatic [18F] trifluoromethyl groups by reacting 1,1-difluorovinyl precursors with [ 18F]fluoride ions, resulting in the equivalent of direct nucleophilic addition of H[18F]F, has been developed. A variety of 18F-labelled model compounds were then obtained and two potential [18F]radiotracers were synthesised by a two step process starting from 1,1-difluorovin-2-yl 4-toluenesulfonate. The method is widely applicable for the synthesis of novel radiotracers in high radiochemical yields and good specific activity.
- Riss, Patrick J.,Aigbirhio, Franklin I.
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supporting information; experimental part
p. 11873 - 11875
(2011/12/04)
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- Facile and efficient synthesis of fluoroalkyl aryl ethers
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A convenient and practical method for the preparation of fluoroalkyl aryl ethers via substitution of iodoalkyl fluorides is described. This method involves KF complexation of the phenol, which increases the nucleophilicity of oxygen for the formation of the ether linkage.
- Kamal, Ahmed,Pratap,Ramana, K.Venkata,Ramana,Babu, A.Hari
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p. 7353 - 7355
(2007/10/03)
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- Syntheses and characterization of 2-amino-5-aryl-1,3,4-oxadiazoles containing trifluoroethoxy groups
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In order to develop an effective synthetic route to 2-amino-5-aryl-1,3,4-oxadiazoles containing trifluoroethoxy groups, a novel intermediate 2-amino-5-[4-(2′,2′,2′-trifluoroethoxy)-phenyl]-1,3,4- oxadiazole was prepared and its structure was confirmed by
- Zhang, Rong,Qian, Xuhong,Li, Zhong
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- Aromatic Fluoroalkoxylation via Direct Displacement of a Nitro or Fluoro Group
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Nitro- and fluorobenzenes substituted with a range of electron-withdrawing groups readily undergo fluoroalkoxylation via direct displacement of the nitro or fluoro group.A number of compounds, which cannot be usefully prepared by direct displacement of a chloro group and which are otherwise inaccessible, have been synthesized.Yields and reaction conditions are comparable to those reported by other workers for reactions involving strong nucleophiles.
- Idoux, John P.,Madenwald, Mark L.,Garcia, Brent S.,Chu, Der-Lun,Gupton, John T.
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p. 1876 - 1878
(2007/10/02)
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- Regioselective fluoroalkoxylation and polyfluoroalkoxylation of aromatic and heteroaromatic polyhalides
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A series of activated polyhalobenzenes and polyhaloheteroaromatic compounds have been reacted with a variety of fluoroalkoxide anions.In most cases, regioselective monosubstitution or polysubstitution was observed.The nature of these monosubstitution and polysubstitution reactions is described.
- Gupton, John T.,Hertel, George,DeCrescenzo, Gary,Colon, Cesar,Baran, Donna,et al.
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p. 3037 - 3042
(2007/10/02)
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- REGIOSELECTIVE FLUOROALKOXYLATION AND POLYFLUOROALKOXYLATION OF ACTIVATED POLYHALOBENZENES
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A series of activated polyhalobenzenes have been reacted with various amounts of sodium 2,2,2-trifluoroethoxide in DMF or HMPA.The nature of these monosubstitution and polysubstitution reactions are described.
- Gupton, John T.,Idoux, John P.,DeCrescenzo, Gary,Colon, Cesar
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p. 621 - 630
(2007/10/02)
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- Aromatic Fluoroalkoxylation via Direct Aromatic Nucleophilic Substitution
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The reaction of activated aryl and heteroaryl halides with fluorinated alkoxide anions is described.In all cases, substitution of the halogen by a fluoroalkoxy group was observed.The effect of solvent, time, temperature, the activating group, leaving group, and the nucleophile on this reaction is also discussed.
- Idoux, John P.,Gupton, John T.,McCurry, Cynthia K.,Crews, A. Donald,Jurss, Cindy D.,et al.
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p. 3771 - 3773
(2007/10/02)
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