- A Series of Deoxyfluorination Reagents Featuring OCF2Functional Groups
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Research on perfluoroalkyl ether carboxylic acids (PFECAs) as alternatives for perfluoroalkyl substances continues with the goal of protecting the environment. However, very little is known about the utilization of decomposition products of PFECAs. We report herein a new series of deoxyfluorination reagents featuring OCF2 functional groups derived from certain PFECAs. Alkyl fluorides were generated from various alcohols in ≤97% yield by these novel reagents. The mechanistic experiment verified in situ generation of carbonic difluoride (COF2).
- Cao, Wei,Chen, Qing-Yun,Guo, Yong,Su, Zhaoben,Wu, Chengying,Zhao, Shiyu
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- A novel fluorinated erythromycin antibiotic
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A novel fluorinated erythromycin (16-fluoroerythromycin A) has been produced by Saccharopolyspora erythraea ERMD1, using precursor-directed biosynthesis. The Royal Society of Chemistry 2005.
- Goss, Rebecca J. M.,Hong, Hui
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- Deoxofluorination reactions using N,N-disubstituted aminodifluorosulfinium tetrafluoroborate salts
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The synthesis of N,N-disubstituted aminodifluorosulfinium tetrafluoroborate salts is reported, and their behavior as deoxofluorinating agent was evaluated. The deoxofluorination reactions were performed using a primary alcohol, a secondary alcohol and a ketone. Results show that subtle modification of the structure of the reagents can noticeably affect the reactivity and the selectivity in deoxofluorination reactions.
- Mahé, Olivier,L'Heureux, Alexandre,Couturier, Michel,Bennett, Christopher,Clayton, Simon,Tovell, David,Beaulieu, Francis,Paquin, Jean-Fran?ois
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- Nickel-Catalyzed Hydrofluorination of Unactivated Alkenes through a HAT Pathway
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We report the hydrofluorination of unactivated alkenes using N-fluorobenzenesulfonimide as a fluorination reagent. The reaction produces exclusively Markovnikov hydrofluorination products under mild conditions. It is not affected by air or moisture and us
- Song, Peihong,Zhu, Shaolin
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- Nucleophilic fluorination using imidazolium based ionic liquid bearing tert-alcohol moiety
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An ionic liquid bearing tert-butanol moiety ([mim-tOH][OMs]) was employed as an organocatalyst in the nucleophilic fluorination of a variety of substrates containing halogen/sulfonate as a leaving group. Low reactive metal fluorides, including KF, were used as a fluoride source in the reaction. Ionic liquid [mim-tOH][OMs] has shown excellent selectivity in nucleophilic fluorination of 2-(3-bromopropyloxy)naphthalene with KF or CsF affording 2-(3-fluoropropyloxy)-naphthalene in high yields. Among the various solvents screened, the activity of alkali metal fluoride was found to be better due to the improved solubility of both the metal fluoride and [mim-tOH][OMs] in the acetonitrile media.
- Shinde, Sandip S.,Patil, Sunil N.,Ghatge, Amruta,Kumar, Pradeep
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- Deoxyfluorination of alcohols with aryl fluorosulfonates
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Aryl fluorosulfonates are developed as a deoxyfluorinating reagent in the transformation of primary and secondary alcohols into the corresponding alkyl fluorides. These reagents feature easy availability, low-cost, high stability and high efficiency. Diverse functionalities including aldehyde, ketone, ester, halogen, nitro, alkene, and alkyne are well tolerated under mild reaction conditions.
- Fei, Zhongbo,Hu, Jinbo,Li, Wei,Liu, Qinghe,Ni, Chuanfa,Wang, Xiu,Zhou, Min
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supporting information
p. 8170 - 8173
(2021/08/23)
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- Nitrogen-phosphine ligand coordination type trifluoromethoxylation reagent, preparation method and application thereof
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The invention discloses a nitrogen-phosphine ligand coordination type trifluoromethoxylation reagent, a preparation method and application thereof. According to the nitrogen-phosphine ligand coordination type trifluoromethoxylation reagent represented by a formula I, a trifluoromethoxy compound is directly prepared by taking primary or secondary p-nitrobenzenesulfonate as a substrate. According tothe invention, the nitrogen-phosphine ligand coordination type trifluoromethoxylation reagent represented by the formula I can inhibit the generation of monofluoro-substituted by-products in an SN2 nucleophilic substitution reaction, so that the trifluoromethoxy compound with high stereospecificity and optical activity is obtained at a high yield.
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Paragraph 0236-0242
(2020/06/17)
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- Alcohol compound-based in-situ deoxygenation fluorination synthesis method and alcohol compound-based F radiolabeling method
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The invention discloses an alcohol compound-based in-situ deoxidation fluorination synthesis method and an alcohol compound-based F radiolabeling method. Alkyl alcohols such as 4-phenyl-1-butanol,which are used as raw materials, react with trifluorome
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Paragraph 0043-0045; 0061-0063
(2020/02/14)
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- Fluorination reagent and deoxygenation fluorination method
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In order to overcome the problems of high cost and poor stability of the existing deoxidation fluorination reagent, the invention provides a fluorination reagent. The fluorination reagent comprises acation M and an anion, and the anion is selected from one or more of the following perfluoropolyether chain carboxylic acid anions: CF3 (OCF2) nCO2, and n is selected from 1-10. Meanwhile, the invention further discloses a deoxidation fluorination method. The fluorination reagent provided by the invention has the advantages that the materials are easy to obtain, the fluorination products can beobtained at higher yield for various alcohol substrates, and the universality for different alcohol substrates is better.
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Paragraph 0066-0116; 0127-0138; 0165-0166
(2020/12/30)
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- Deoxyfluorination with CuF2: Enabled by Using a Lewis Base Activating Group
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Deoxyfluorination is a primary method for the formation of C?F bonds. Bespoke reagents are commonly used because of issues associated with the low reactivity of metal fluorides. Reported here is the development of a simple strategy for deoxyfluorination, using first-row transition-metal fluorides, and it overcomes these limitations. Using CuF2 as an exemplar, activation of an O-alkylisourea adduct, formed in situ, allows effective nucleophilic fluoride transfer to a range of primary and secondary alcohols. Spectroscopic investigations have been used to probe the origin of the enhanced reactivity of CuF2. The utility of the process in enabling 18F-radiolabeling is also presented.
- Bode, Bela E.,Chabbra, Sonia,Champion, Sue,Dawson, Daniel M.,Sood, D. Eilidh,Sutherland, Andrew,Watson, Allan J. B.
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supporting information
p. 8460 - 8463
(2020/04/10)
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- Photoredox-catalyzed deoxyfluorination of activated alcohols with Selectfluor
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Herein we disclose a deoxyfluorination of alcohols with an electrophilic fluorine source via visible-light photoredox catalysis. This radical-mediated C–F coupling is capable of fluorinating secondary and tertiary alcohols efficiently, complementing previously reported nucleophilic deoxyfluorination protocols.
- González-Esguevillas, María,Miró, Javier,Jeffrey, Jenna L.,MacMillan, David W.C.
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supporting information
p. 4222 - 4227
(2019/06/13)
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- Rapid Deoxyfluorination of Alcohols with N-Tosyl-4-chlorobenzenesulfonimidoyl Fluoride (SulfoxFluor) at Room Temperature
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The deoxyfluorination of alcohols is a fundamentally important approach to access alkyl fluorides, and thus the development of shelf-stable, easy-to-handle, fluorine-economical, and highly selective deoxyfluorination reagents is highly desired. This work describes the development of a crystalline compound, N-tosyl-4-chlorobenzenesulfonimidoyl fluoride (SulfoxFluor), as a novel deoxyfluorination reagent that possesses all of the aforementioned merits, which is rare in the arena of deoxyfluorination. Endowed by the multi-dimensional modulating ability of the sulfonimidoyl group, SulfoxFluor is superior to 2-pyridinesulfonyl fluoride (PyFluor) in fluorination rate, and is also superior to perfluorobutanesulfonyl fluoride (PBSF) in fluorine-economy. Its reaction with alcohols not only tolerates a wide range of functionalities including the more sterically hindered alcoholic hydroxyl groups, but also exhibits high fluorination/elimination selectivity. Because SulfoxFluor can be easily prepared from inexpensive materials and can be safely handled without special techniques, it promises to serve as a practical deoxyfluorination reagent for the synthesis of various alkyl fluorides.
- Guo, Junkai,Kuang, Cuiwen,Rong, Jian,Li, Lingchun,Ni, Chuanfa,Hu, Jinbo
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supporting information
p. 7259 - 7264
(2019/05/10)
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- Halogenation through Deoxygenation of Alcohols and Aldehydes
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An efficient reagent system, Ph3P/XCH2CH2X (X = Cl, Br, or I), was very effective for the deoxygenative halogenation (including fluorination) of alcohols (including tertiary alcohols) and aldehydes. The easily available 1,2-dihaloethanes were used as key reagents and halogen sources. The use of (EtO)3P instead of Ph3P could also realize deoxy-halogenation, allowing for a convenient purification process, as the byproduct (EtO)3Pa?O could be removed by aqueous washing. The mild reaction conditions, wide substrate scope, and wide availability of 1,2-dihaloethanes make this protocol attractive for the synthesis of halogenated compounds.
- Chen, Jia,Lin, Jin-Hong,Xiao, Ji-Chang
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supporting information
p. 3061 - 3064
(2018/05/28)
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- Stereospecific Electrophilic Fluorination of Alkylcarbastannatrane Reagents
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We report the use of isolable primary and secondary alkylcarbastannatrane nucleophiles in site-specific fluorination reactions. These reactions occur without the need for transition metal catalysis or in situ activation of the nucleophile. In the absence of the carbastannatrane backbone, alkyltin nucleophiles exhibit no activity towards fluorination. When enantioenriched alkylcarbastannatranes are employed, fluorination occurs predominately via a stereoinvertive mechanism to generate highly enantioenriched alkyl fluoride compounds. These conditions can also be extended to stereospecific chlorination, bromination, and iodination reactions.
- Ma, Xinghua,Diane, Mohamed,Ralph, Glenn,Chen, Christine,Biscoe, Mark R.
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supporting information
p. 12663 - 12667
(2017/09/11)
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- Hypervalent Iodine-Based Activation of Triphenylphosphine for the Functionalization of Alcohols
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The use of hypervalent iodine reagents as a general tool for the activation of PPh 3 and its application to the functionalization of alcohols is reported. Combination of PPh 3 with PhICl 2 or TolIF 2 gives dihalophosphoranes that are characterized by 31 P NMR, however, with PhIOAc 2, PhI(OTFA) 2, or the cyclic chloro(benzoyloxy)iodane, no phosphoranes were observed. Reaction of these iodanes with PPh 3 in the presence of primary, secondary, or tertiary alcohols results in either halogenation or acyl-transfer products in moderate to high yield.
- Eljo, Jasmin,Carle, Myriam S.,Murphy, Graham K.
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supporting information
p. 2871 - 2875
(2017/10/06)
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- Direct dehydroxytrifluoromethylthiolation of alcohols using silver(I) trifluoromethanethiolate and tetra-n-butylammonium iodide
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An unprecedented reaction for the direct trifluoromethylthiolation and fluorination of alkyl alcohols using AgSCF3 and nBu4NI has been developed. The trifluoromethylthiolated compounds and alkyl fluorides were selectively formed by c
- Liu, Jian-Bo,Xu, Xiu-Hua,Chen, Zeng-Hao,Qing, Feng-Ling
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p. 897 - 900
(2015/02/05)
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- PyFluor: A low-cost, stable, and selective deoxyfluorination reagent
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We report an inexpensive, thermally stable deoxyfluorination reagent that fluorinates a broad range of alcohols without substantial formation of elimination side products. This combination of selectivity, safety, and economic viability enables deoxyfluorination on preparatory scale. We employ the [18F]-labeled reagent in the first example of a no-carrier-added deoxy-radiofluorination.
- Nielsen, Matthew K.,Ugaz, Christian R.,Li, Wenping,Doyle, Abigail G.
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supporting information
p. 9571 - 9574
(2015/08/18)
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- An easy access to fluoroalkanes by deoxygenative hydrofluorination of carbonyl compounds via their tosylhydrazones
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An efficient and operationally simple synthesis of fluoroalkanes by deoxygenative hydrofluorination of carbonyl compounds via their tosylhydrazone surrogates is reported. The reaction can be carried out in a one-pot procedure directly from carbonyl compounds.
- Yadav, Arvind K.,Srivastava, Vishnu P.,Yadav, Lal Dhar S.
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supporting information
p. 2154 - 2156
(2013/03/14)
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- Efficient SN2 fluorination of primary and secondary alkyl bromides by copper(I) fluoride complexes
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Copper(I) fluoride complexes ligated by phenanthroline derivatives have been synthesized and structurally characterized by X-ray crystallography. These complexes adopt as either ionic or neutral forms in the solid state, depending on the steric bulkiness of the substituent groups on the phenanthroline ligands. These complexes react with primary and secondary alkyl bromides to produce the corresponding alkyl fluorides in modest to good yields. This new method is compatible with a variety of important functional groups such as ether, thioether, amide, nitrile, methoxyl, hydroxyl, ketone, ester, and heterocycle moieties.
- Liu, Yanpin,Chen, Chaohuang,Li, Huaifeng,Huang, Kuo-Wei,Tan, Jianwei,Weng, Zhiqiang
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p. 6587 - 6592
(2013/12/04)
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- Fe(III)/NaBH4-mediated free radical hydrofluorination of unactivated alkenes
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A powerful Fe(III)/NaBH4-mediated free radical hydrofluorination of unactivated alkenes is disclosed using Selectfluor reagent as a source of fluorine and resulting in exclusive Markovnikov addition. In contrast to the traditional and unmanageable free radical hydrofluorination of alkenes, the Fe(III)/NaBH4-mediated reaction is conducted under exceptionally mild reaction conditions (0 °C, 5 min, CH3CN/H2O). The reaction can be conducted open to the air and with water as a cosolvent and demonstrates an outstanding substrate scope and functional group tolerance.
- Barker, Timothy J.,Boger, Dale L.
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supporting information; experimental part
p. 13588 - 13591
(2012/10/08)
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- Fluorine transfer to alkyl radicals
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The development of new synthetic technologies for the selective fluorination of organic compounds has increased with the escalating importance of fluorine-containing pharmaceuticals. Traditional methods potentially applicable to drug synthesis rely on the use of ionic forms of fluorine (F - or F+). Radical methods, while potentially attractive as a complementary approach, are hindered by a paucity of safe sources of atomic fluorine (F?). A new approach to alkyl fluorination has been developed that utilizes the reagent N-fluorobenzenesulfonimide as a fluorine transfer agent to alkyl radicals. This approach is successful for a broad range of alkyl radicals, including primary, secondary, tertiary, benzylic, and heteroatom-stabilized radicals. Furthermore, calculations reveal that fluorine-containing ionic reagents are likely candidates for further expansion of this approach to polar reaction media. The use of these reagents in alkyl radical fluorination has the potential to enable powerful new transformations that otherwise would take multiple synthetic steps.
- Rueda-Becerril, Montserrat,Chatalova Sazepin, Claire,Leung, Joe C. T.,Okbinoglu, Tulin,Kennepohl, Pierre,Paquin, Jean-Francois,Sammis, Glenn M.
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p. 4026 - 4029
(2012/04/10)
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- Aminodifluorosulfinium salts: Selective fluorination reagents with enhanced thermal stability and ease of handling
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Diethylaminodifluorosulfinium tetrafluoroborate (XtalFluor-E) and morpholinodifluorosulfinium tetrafluoroborate (XtalFluor-M) are crystalline fluorinating agents that are more easily handled and significantly more stable than Deoxo-Fluor, DAST, and their analogues. These reagents can be prepared in a safer and more cost-efficient manner by avoiding the laborious and hazardous distillation of dialkylaminosulfur trifluorides. Unlike DAST, Deoxo-Fluor, and Fluolead, XtalFluor reagents do not generate highly corrosive free-HF and therefore can be used in standard borosilicate vessels. When used in conjunction with promoters such as Et3N3HF, Et3N2HF, or DBU, XtalFluor reagents effectively convert alcohols to alkyl fluorides and carbonyls to gem-difluorides. These reagents are typically more selective than DAST and Deoxo-Fluor and exhibit superior performance by providing significantly less elimination side products.
- Lheureux, Alexandre,Beaulieu, Francis,Bennett, Christopher,Bill, David R.,Clayton, Simon,Laflamme, Franois,Mirmehrabi, Mahmoud,Tadayon, Sam,Tovell, David,Couturier, Michel
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supporting information; experimental part
p. 3401 - 3411
(2010/07/07)
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- DISUBSTITUTED-AMINODIFLUOROSULFINIUM SALTS, PROCESS FOR PREPARING SAME AND METHOD OF USE AS DEOXOFLUORINATION REAGENTS
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The invention relates to disubstituted-aminodifluorosulfinium salts represented by the formula (I). Processes for preparing same and methods of use as deoxofluorinating reagent is also provided.
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Page/Page column 40
(2010/12/31)
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- Nucleophilic fluorination of triflates by tetrabutylammonium bifluoride
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(Chemical Equation Presented) Careful examination of nucleophilicity, basicity, and leaving group ability led us to discover the nucleophilic fluorination of triflates by weakly basic tetrabutylammonium bifluoride, which provides excellent yields with minimal formation of elimination-derived side products. Primary hydroxyl groups as well as secondary hydroxyl groups in acyclic chains or in five-membered rings are excellent substrates, whereas benzylic and aldol-type secondary hydroxyl groups give poor yields as a result of the instability of their triflates.
- Kim, Kyu-Young,Bong, Chan Kim,Hee, Bong Lee,Shin, Hyunik
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p. 8106 - 8108
(2008/12/22)
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- Direct and convenient conversion of alcohols to fluorides
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Directly mixing primary, secondary, and tertiary alcohols with nC 4F9SO2F-NR3(HF)3-NR 3 in THF or MeCN results in convenient conversion to the corresponding fluorides in high yields. The readily available reagents are easy to handle, and the mild, almost neutral reaction conditions allow for excellent functional group compatibility. A NR3(HF)3/NR3 ratio of ≤ 1:2 gives the highest reactivity.
- Yin, Jingjun,Zarkowsky, Devin S.,Thomas, David W.,Zhao, Matthew M.,Huffman, Mark A.
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p. 1465 - 1468
(2007/10/03)
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- Et3n .2Hf, a new convenient reagent for nucleophilic fluorine displacement reactions
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Syntheses of fluoro compounds by nucleophilic substitution of bromides or methane sulfonates using Et3N .2HF as the reagent are reported. The formation of undesired elimination side products is limited. The synthesis of this new fluorinating reagent is also reported.
- Giudicelli,Pica,Veyron
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p. 6527 - 6530
(2007/10/02)
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