- A Carbene Strategy for Progressive (Deutero)Hydrodefluorination of Fluoroalkyl Ketones
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Hydrodefluorination is one of the most promising chemical strategies to degrade perfluorochemicals into partially fluorinated compounds. However, controlled progressive hydrodefluorination remains a significant challenge, owing to the decrease in the stre
- Bi, Xihe,Sivaguru, Paramasivam,Song, Qingmin,Wang, Zikun,Zanoni, Giuseppe,Zhang, Xiaolong,Zhang, Xinyu
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- Unbalanced-Ion-Pair-Catalyzed Nucleophilic Fluorination Using Potassium Fluoride
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An unbalanced ion pair promoter (e.g., tetrabutylammonium sulfate), consisting of a bulky and charge-delocalized cation and a small and charge-localized anion, greatly accelerates nucleophilic fluorinations using easy handling KF. We also successfully converted an inexpensive and commercially available ion-exchange resin to the polymer-supported ion pair promoter (A26–SO42–), which could be reused after filtration. Moreover, A26–SO42– can be used in continuous flow conditions. In our conditions, water is well-tolerated.
- Hammond, Gerald B.,Li, Wangbing,Lu, Zhichao,Xu, Bo
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supporting information
p. 9640 - 9644
(2021/12/14)
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- Α - fluoro acetophenone derivative
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PROBLEM TO BE SOLVED: To provide a new production method of an α-fluoroacetophenone derivative by a simple one-step fluorination reaction with an acetophenone derivative under a mild condition.SOLUTION: An acetophenone derivative represented by formula (I) is reacted with a hydrogen fluoride/amine complex in the presence of a hypervalent iodine compound, (in the formula, a ring A indicates an aromatic ring of 1-3 members; Rindicates a hydrogen atom or an aromatic ring of 1-3 members that may be substituted; Rindicates a hydrogen atom or an alkyl group of 1-6 carbons; and Rindicates a hydrogen atom, an alkyl group of 1-6 carbons, an alkoxy group of 1-6 carbons or a halogen atom). The H part in formula (I) is substituted and fluorinated.
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Paragraph 0029; 0038
(2018/08/28)
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- Pyrene-Tagged Ionic Liquids: Separable Organic Catalysts for SN2 Fluorination
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We prepared pyrene-substituted imidazolium-based ionic liquids (PILs) as organic catalysts for the SN2 fluorination using alkali metal fluoride (MF). In this system, the PIL significantly enhanced the reactivity of MF due to the phase-transfer
- Taher, Abu,Lee, Kyo Chul,Han, Hye Ji,Kim, Dong Wook
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supporting information
p. 3342 - 3345
(2017/07/15)
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- Synthesis of α-Fluoroketones by Insertion of HF into a Gold Carbene
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Reported is an efficient synthesis of α-fluoroketones by insertion of hydrogen fluoride (HF) into the gold carbene intermediate, generated from a cationic gold catalyzed addition of N-oxides to alkynes. This method results in excellent chemical yields for a wide range of alkyne substrates and demonstrates good functional-group tolerance.
- Zeng, Xiaojun,Liu, Shiwen,Shi, Zhenyu,Liu, Guangchang,Xu, Bo
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supporting information
p. 10032 - 10036
(2016/08/16)
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- Synthesis of α-Fluoroketones from Vinyl Azides and Mechanism Interrogation
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An efficient and mild fluorination of vinyl azides for the synthesis of α-fluoroketones is described. The mechanistic studies indicated that a single-electron transfer (SET) and a subsequent fluorine atom transfer process could be involved in the reaction.
- Wu, Shu-Wei,Liu, Feng
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p. 3642 - 3645
(2016/08/16)
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- A Practical Synthesis of α-Fluoroketones in Aqueous Media by Decarboxylative Fluorination of β-Ketoacids
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A practical and novel process for the decarboxylative fluorination of β-ketoacids in water in the presence of phase transfer catalyst has been developed, affording a series of α-fluoroketones in good to excellent yields. Furthermore, a preliminary investigation for the catalytic asymmetric transformation was performed and a proposed mechanistic pathway for this catalytic process was proposed.
- Li, Jian,Li, Yin-Long,Jin, Nan,Ma, Ai-Lun,Huang, Ya-Nan,Deng, Jun
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supporting information
p. 2474 - 2478
(2015/08/18)
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- Hypervalent iodine-promoted α-fluorination of acetophenone derivatives with a triethylamine·hf complex
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The direct fluorination reaction of acetophenone using iodosylarenes and TEA·5HF was conducted under mild conditions except for use of a HF reagent. The fluorination reaction was applied to acetophenone derivatives, acetonaphthones, benzyl phenyl ketone, propiophenone, butyrophenone, 1-indanone, and phenacyl chloride, giving selectively the corresponding α-fluoroketone derivatives in good yields.
- Kitamura, Tsugio,Muta, Kensuke,Muta, Kazutaka
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p. 5842 - 5846
(2014/07/08)
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- Oligoethylene glycols as highly efficient mutifunctional promoters for nucleophilic-substitution reactions
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Herein, we report the promising use of n-oligoethylene glycols (oligoEGs) as mutifunctional promoters for nucleophilic-substitution reactions employing alkali metal salts. Among the various oligoEGs tested, pentaethylene glycol (pentaEG) had the most efficient catalytic activity. In particular, when compared with other nucleophiles examined, a fluorine nucleophile generated from CsF was significantly activated by the pentaEG promoter. We also performed various facile nucleophilic-displacement reactions, such as the halogenation, acetoxylation, thioacetoxylation, nitrilation, and azidation of various substrates with potassium halides, acetate, thioacetate, cyanide, and sodium azide, respectively, in the presence of the pentaEG promoter. All of these reactions provided their desired products in excellent yields. Furthermore, the combination of pentaEG and a tert-alcohol medium showed tremendous efficiency in the nucleophilic-displacement reactions (fluorination and methoxylation) of base-sensitive substrates with basic nucleophiles (cesium fluoride and potassium methoxide, respectively). The catalytic role of oligoEGs was examined by quantum-chemical methods. The oxygen atoms in oligoEGs were found to act as Lewis bases on the metal cations to produce the "flexible" nucleophile, whereas the two terminal hydroxy (OH) groups acted as "anchors" to orientate the nucleophile and the substrate into an ideal configuration for the reaction. The EG race: OligoEGs, such as pentaethylene glycol (pentaEG), act as mutifunctional promoters for nucleophilic-substitution reactions with the corresponding alkali-metal salts. The combination of pentaEG and a tert-alcohol media system showed tremendous efficiency in the fluorination and methoxylation of base-sensitive substrates by using the corresponding basic nucleophiles (see figure). Copyright
- Jadhav, Vinod H.,Jang, Seung Ho,Jeong, Hwan-Jeong,Lim, Seok Tae,Sohn, Myung-Hee,Kim, Ju-Young,Lee, Sungyul,Lee, Ji Woong,Song, Choong Eui,Kim, Dong Wook
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supporting information; experimental part
p. 3918 - 3924
(2012/06/01)
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- Tailor-made hexaethylene glycolic ionic liquids as organic catalysts for specific chemical reactions
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Chemical equations presented. Hexaethylene glycol substituted imidazolium based ionic liquids (hexaEGILs) were designed and prepared well-tailored to a specific organic reaction using alkali-metal fluorides (MFs) as multifunctional organic catalysts. These hexaEGIL catalysts could significantly enhance the reactivity of MF, even KF. Furthermore, the hexaEGIL systems showed tremendous efficiency in the nucleophilic fluorination of base-sensitive substrates.
- Jadhav, Vinod H.,Jeong, Hwan-Jeong,Lim, Seok Tae,Sohn, Myung-Hee,Kim, Dong Wook
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supporting information; experimental part
p. 2502 - 2505
(2011/07/09)
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- Polymer-supported pentaethylene glycol as a facile heterogeneous catalyst for nucleophilic fluorination
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Polymer-supported pentaethylene glycols (PSpentaEG) as promising catalysts for nucleophilic fluorination with alkali metal fluoride (MF) could significantly enhance the nucleophilicity of MF and provide simple purification and recycling in the reaction. F
- Jadhav, Vinod H.,Jang, Seung Ho,Jeong, Hwan-Jeong,Lim, Seok Tae,Sohn, Myung-Hee,Chi, Dae Yoon,Kim, Dong Wook
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supporting information; experimental part
p. 3740 - 3743
(2010/11/05)
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- TAMING ELEMENTAL FLUORINE: INDIRECT USE OF FLUORINE FOR THE SYNTHESIS OF α-FLUOROKETONES
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Fluorine and sodium trifloroacetate react at -75 deg to produce a variety of fluoroxy-compounds.Although it is possible to direct the reaction towards the formation of CF3COOF or CF3CF2O, mixtures may be used when only the electrophilic fluorine has to be
- Rozen Shlomo,Menahem, Ynon
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