- Fluorinations of unsymmetrical diaryliodonium salts containing: Ortho -sidearms; Influence of sidearm on selectivity
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Activated aromatics were reacted with two different fluoroidoane reagents 1 and 2 in the presence of triflic acid to prepare only the para-substituted diaryliodonium salts. With fluoroiodane 1 the unsymmetrical diaryliodonium salts contained an ortho-propan-2-ol sidearm, whereas the alcohol sidearm was eliminated to form an ortho-styrene sidearm in the reaction with fluoroiodane 2. Only the diaryliodonium salts containing a styrene sidearm were fluorinated successfully to deliver para-fluorinated aromatics in good yields.
- Abudken, Ahmed M. H.,Hope, Eric G.,Singh, Kuldip,Stuart, Alison M.
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supporting information
p. 6140 - 6146
(2020/10/30)
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- Studying regioisomer formation in the pd-catalyzed fluorination of aryl triflates by deuterium labeling
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Isotopic labeling has been used to determine that a portion of the desired product in the Pd-catalyzed fluorination of electron-rich, non-ortho-substituted aryl triflates results from direct C-F cross-coupling. In some cases, formation of a Pd-aryne intermediate is responsible for producing undesired regioisomers. The generation of the Pd-aryne intermediate occurs primarily via ortho-deprotonation of a L·Pd(Ar)OTf (L = biaryl monophosphine) species by CsF and thus competes directly with the transmetalation step of the catalytic cycle. Deuterium labeling studies were conducted with a variety of aryl triflates.
- Milner, Phillip J.,Kinzel, Tom,Zhang, Yong,Buchwald, Stephen L.
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supporting information
p. 15757 - 15766
(2015/02/02)
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- Mild copper-mediated fluorination of aryl stannanes and aryl trifluoroborates
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This communication describes a mild copper-mediated fluorination of aryl stannanes and aryl trifluoroborates with N-fluoro-2,4,6-trimethylpyridinium triflate. This protocol demonstrates broad substrate scope and functional group tolerance, and does not require the use of any noble metal additives. The reaction is proposed to proceed via an arylcopper(III) fluoride intermediate.
- Ye, Yingda,Sanford, Melanie S.
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supporting information
p. 4648 - 4651
(2013/05/09)
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- Electrophilic fluorination of cationic Pt-aryl complexes
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The electrophilic fluorination of several (triphos)Pt-aryl+ establishes the first example of aryl-F coupling from a Pt center.
- Zhao, Shu-Bin,Wang, Rui-Yao,Nguyen, Ha,Becker, Jennifer J.,Gagne, Michel R.
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supporting information; experimental part
p. 443 - 445
(2012/01/14)
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- Metal-Catalyzed Carbon-Fluorine Bond Formation
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One aspect of the invention relates to a metal-catalyzed conversion of aryl halides and sulfonates to the corresponding aryl fluorides. Another aspect of the invention relates to a metal-catalyzed conversion of heteroaryl halides and sulfonates to the corresponding heteroaryl fluorides. Another aspect of the invention relates to a metal-catalyzed conversion of vinyl halides and sulfonates to the corresponding vinyl fluorides. In certain embodiments, simple fluoride sources, such as AgF and CsF, are used. In certain embodiments, the transformations tolerate a wide range of functional groups, allowing for introduction of fluorine atoms into highly functionalized organic molecules.
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Page/Page column 18
(2011/02/18)
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- Fluorination of aromatic compounds with N-fluorobenzenesulfonimide under solvent-free conditions
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Reactions of N-fluorobenzenesulfonimide with methylbenzenes, phenols, and phenol ethers were studied under solvent-free conditions. The rate constant ratio for the reactions with mesitylene and durene indicates polar mechanism of the process. Solvent-free fluorination of aromatic compounds with N-fluorobenzenesulfonimide in some cases is more selective than reactions with other N-F reagents in a solvent.
- Andreev,Borodkin,Shubin
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scheme or table
p. 1468 - 1473
(2010/03/24)
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- Preparation process of fluorine substituted aromatic compound
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A preparation process of a fluorine substituted aromatic compound comprising reacting an alkali metal or alkali earth metal salt of an aromatic compound having a hydroxy group with an organic fluorinating agent is disclosed. As a representative fluorinating agent, a bis-dialkylamino-difluoromethane compound, for example, 2,2′-difluoro-1,3-dimethylimidazolidine, is exemplified. According to the process, an industrially useful fluorinated aromatic compound, for example, a fluorobenzene, a fluorine substituted benzophenone, a fluorine substituted diarylsulfone can be prepared with ease in economy without specific equipment.
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- Process for the preparation of fluoro compounds from the corresponding amines
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Compounds containing a primary amino group are converted into compounds containing a fluorine atom in place of the amino group by reaction of the amino compound with hydrogen fluoride and a nitrosating reagent under the influence of ultrasound or microwaves.
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- Process for preparing o-alkylfluorobenzenes
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o-Alkylfluorobenzenes are advantageously prepared by heating the corresponding chloroformates to from 70° to 200° C. in the liquid phase in the presence of hydrogen fluoride and in the presence of an inert diluent other than a halogenated alkane.
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- Liquid-Phase Decarboxylation of Aromatic Haloformates: A New Access to Chloro- and Fluoroaromatics
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The treatment of phenyl chloroformates 1 with a Lewis acid in the liquid phase resulted in decarboxylation to the corresponding chloroaromatics 2. Fluoroaromatic compounds were synthesized from phenylchloroformates 1 through a sequential fluorination/decarboxylation in the liquid phase by treatment with excess anhydrous hydrogen fluoride under mild conditions. In all cases, yields were increased by performing the reaction in 1,2,4-trichlorobenzene, which is inert to Friedel-Crafts reactions.
- Lui, Norbert,Marhold, Albrecht,Rock, Michael H.
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p. 2493 - 2496
(2007/10/03)
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- Aryl fluoride syntheses involving reactions of aryllead triacetates with boron trifluoride-diethyl ether complex
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Aryllead(IV) triacetates react at room temperature with BF3.Et2O to give the corresponding aryl fluoride in moderate to good yields; triarylboroxines, electron rich aryltrimethylsilanes and some arenes, which yield aryllead triacetates in acid catalysed reactions with lead tetraacetate, are converted directly into aryl fluorides when stirred with lead tetraacetate in BF3.Et2O. An investigation of the mechanism of the fluoro-deplumbation reaction indicates that it probably proceeds by acid catalysed heterolytic cleavage of the C-Pb bond to produce an aryl cation.
- De Meio,Morgan,Pinhey
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p. 8129 - 8138
(2007/10/02)
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- Phosphorus-fluorine chemistry. XIII. The adduct of nitrosyl fluoride with phenyltetrafluorophosphorane. New fluorophosphates
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Nitrosyl fluoride was found to react with phenyltetrafluorophosphorane to form a solid, thermally unstable 1:1 adduct. Evidence for the formulation of this adduct as a nitrosyl salt, NO+C6H5PF5-, based on various chemical reactions, is presented. The novel fluoroanions, R(Ar)PF5-, together with alkyl(aryl)dialkylaminotrifluorophosphoranes, R(Ar)PF3NR2, are also obtained in the form of stable dialkylammonium salts upon dialkylaminolysis of tetrafluorophosphoranes, R(Ar)PF4. The stereochemistry of the R(Ar)PF5- anions, and of the alkyl(aryl)dialkylaminotrifluorophosphoranes, based on n.m.r. spectroscopic studies, is discussed. In contrast to nitrosyl fluoride, nitryl fluoride reacted with phenyltetrafluorophosphorane with direct nitration of the aromatic ring.
- Schmutzler,Reddy
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p. 191 - 197
(2007/10/04)
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