- PROCESSES FOR FLUORINATION
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The present technology relates to fluorination reactions. Specifically, processes useful for making the fungicide compound, DFT are disclosed. More broadly, also disclosed herein are processes useful for deoxyfluorination at the α-aromatic position of a given compound.
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Paragraph 0179; 0184; 0214-0215; 0217
(2021/04/10)
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- 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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supporting information
(2020/11/03)
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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; 0145-0146
(2020/12/30)
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- Cobalt-Catalyzed Asymmetric Cross-Coupling Reaction of Fluorinated Secondary Benzyl Bromides with Lithium Aryl Boronates/ZnBr2
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A cobalt-catalyzed asymmetric cross-coupling of α-bromo-α-fluorotoluene derivatives with a variety of aryl zincates derived from lithium aryl n-butyl pinacol boronates and ZnBr2 under mild reaction conditions was described. In addition to mild reaction conditions, another advantage includes the compatibility of various common functional groups such as fluoride, chloride, bromide, cyano, or ester groups. Furthermore, this protocol was successfully applied to the enantioselective synthesis of three fluorinated derivatives of biologically active compounds or drug molecules.
- Huang, Weichen,Shen, Qilong,Wan, Xiaolong
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supporting information
p. 4327 - 4332
(2020/06/27)
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- Thiourea-Catalyzed C?F Bond Activation: Amination of Benzylic Fluorides
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We describe the first thiourea-catalyzed C?F bond activation. The use of a thiourea catalyst and Ti(OiPr)4 as a fluoride scavenger allows the amination of benzylic fluorides to proceed in moderate to excellent yields. Preliminary results with S- and O-based nucleophiles are also presented. DFT calculations reveal the importance of hydrogen bonds between the catalyst and the fluorine atom of the substrate to lower the activation energy during the transition state.
- Houle, Camille,Savoie, Paul R.,Davies, Clotilde,Jardel, Damien,Champagne, Pier Alexandre,Bibal, Brigitte,Paquin, Jean-Fran?ois
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p. 10620 - 10625
(2020/07/24)
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- Copper-Catalyzed C-H Fluorination/Functionalization Sequence Enabling Benzylic C-H Cross Coupling with Diverse Nucleophiles
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Site-selective transformation of benzylic C-H bonds into diverse functional groups is achieved via Cu-catalyzed C-H fluorination with N-fluorobenzenesulfonimide (NFSI), followed by substitution of the resulting fluoride with various nucleophiles. The benzyl fluorides generated in these reactions are reactive electrophiles in the presence of hydrogen-bond donors or Lewis acids, allowing them to be used without isolation in C-O, C-N, and C-C coupling reactions.
- Buss, Joshua A.,Golden, Dung L.,Stahl, Shannon S.,Vasilopoulos, Aristidis
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supporting information
(2020/08/24)
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- PROCESSES FOR FLUORINATION
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The present technology relates to fluorination reactions. Specifically, processes useful for making the fungicide compound, DFT are disclosed. More broadly, also disclosed herein are processes useful for deoxyfluorination at the α-aromatic position of a given compound.
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Paragraph 0188
(2020/03/05)
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- Nucleophilic Substitution of Aliphatic Fluorides via Pseudohalide Intermediates
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A method for aliphatic fluoride functionalization with a variety of nucleophiles has been reported. Carbon–fluoride bond cleavage is thermodynamically driven by the use of silylated pseudohalides TMS-OMs or TMS-NTf2, resulting in the formation of TMS-F and a trapped aliphatic pseudohalide intermediate. The rate of fluoride/pseudohalide exchange and the stability of this intermediate are such that little rearrangement is observed for terminal fluoride positions in linear aliphatic fluorides. The ability to convert organofluoride positions into pseudohalide groups allows facile nucleophilic attack by a wide range of nucleophiles. The late introduction of the nucleophiles also allows for a wide range of functional-group tolerance in the coupling partners. Selective alkyl fluoride mesylation is observed in the presence of other alkyl halides, allowing for orthogonal synthetic strategies.
- Jaiswal, Amit K.,Prasad, Pragati K.,Young, Rowan D.
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supporting information
p. 6290 - 6294
(2019/04/26)
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- Nickel-catalyzed monofluoromethylation of aryl boronic acids
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Aryl boronic acids can be monofluoromethylated under nickel catalysis. The utility of this method is demonstrated by the monofluoromethylation of a borylated and acyl-protected derivative of the statin drug ezetimibe. Mechanistic investigations indicate that a fluoromethyl radical is involved in the NiI/NiIII catalytic cycle.
- Su, Yi-Ming,Feng, Guang-Shou,Wang, Zhen-Yu,Lan, Quan,Wang, Xi-Sheng
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p. 6003 - 6007
(2015/05/13)
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- A convenient route to tetraalkylammonium perfluoroalkoxides from hydrofluoroethers
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Hydrofluoroethers are shown to alkylate tertiary amines readily under solvent-free conditions, affording valuable tetraalkylammonium perfluoroalkoxides bearing α-fluorines. The reaction of RFCF2-OCH3 (RF = CF2CF3, CF2CF2CF3, and CF(CF3)2) with NR1R2R3 produces twenty new α-perfluoroalkoxides, [(CH3)NR1R2R3][RFCF2O] under mild conditions. These α-perfluoroalkoxides are easy to handle, thermally stable, and can be used for the perfluoroalkoxylation of benzyl bromides.
- Jelier, Benson J.,Leznoff, Daniel B.,Howell, Jon L.,Montgomery, Craig D.,Friesen, Chadron M.
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supporting information
p. 2945 - 2949
(2015/05/12)
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- Enabling nucleophilic substitution reactions of activated alkyl fluorides through hydrogen bonding
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It was discovered that the presence of water as a cosolvent enables the reaction of activated alkyl fluorides for bimolecular nucleophilic substitution reactions. DFT calculations show that activation proceeds through stabilization of the transition structure by a stronger F···H 2O interaction and diminishing C-F bond elongation, and not simple transition state electrostatic stabilization. Overall, the findings put forward a distinct strategy for C-F bond activation through H-bonding.
- Champagne, Pier Alexandre,Pomarole, Julien,Therien, Marie-Eve,Benhassine, Yasmine,Beaulieu, Samuel,Legault, Claude Y.,Paquin, Jean-Francois
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p. 2210 - 2213
(2013/06/26)
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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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- Electrochemical fluorination using halogen mediators in ionic liquid hydrogen fluoride salt
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In order to utilize ammomium halides (Et4NX, X=Cl, Br, I) as halogenmediator for electrocatalytic fluorination, cyclic voltammetry measurements of the halides were investigated. The catalytic current of the halides in the presence of a dithioacatal compound was observed and the macro-scale electrolysis of dithioacetals using the halogen mediator was also carried out in ionic liquid hydrogen fluoride (HF) salt to give the corresponding fluorinated products in excellent yields. The recycle use of the halogen mediator in the electrochemical fluorination was successfully demonstrated. More inexpensive halides such as potassium bromide and potassium iodide could be soluble in HF salt and worked well as halogen mediator for the electrocatalytic fluorination.
- Takahashi, Kohta,Inagi, Shinsuke,Fuchigami, Toshio
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p. G3046-G3052
(2013/07/05)
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- Recyclable polymer-supported iodobenzene-mediated electrocatalytic fluorination in ionic liquid
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The electrochemical fluorination of organosulfur compounds in triethylamine/hydrofluoric acid (Et3N-5HF) with polystyrene-supported iodobenzene (PSIB) and tetraethylammonium chloride (Et4NCl) was performed successfully in an undivided cell under constant current conditions to afford the corresponding fluorinated compounds in moderate to good yields. Recycle use of the PSIB could be achieved due to its easy separation. Notably, the mediatory activity of the iodobenzene derivative was not appreciably changed even after 10 recycle uses.
- Sawamura, Takahiro,Kuribayashi, Shunsuke,Inagi, Shinsuke,Fuchigami, Toshio
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experimental part
p. 2757 - 2760
(2010/12/25)
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- Deoxyfluorination of alcohols using N,N-diethyl-α,α-difluoro- (m-methylbenzyl)amine
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Deoxyfluorination of alcohols was carried out using N,N-diethyl-α, α-difluoro-(m-methylbenzyl)amine (DFMBA). Primary alcohols were effectively converted to fluorides under microwave irradiation or conventional heating. Deoxyfluorination of an anomeric hydroxy group in sugars by DFMBA proceeded at below room temperature and glycosyl fluorides could be obtained in good yields. The deoxyfluorination reaction chemoselectively proceeded and various protecting groups on the sugar can survive under the reaction conditions.
- Kobayashi, Shingo,Yoneda, Atushi,Fukuhara, Tsuyoshi,Hara, Shoji
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p. 6923 - 6930
(2007/10/03)
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- Efficient and selective halogenation of allylic and benzylic alcohols under mild conditions
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A simple, mild, and high yielding procedure for the halogenation of allylic and benzylic alcohols using a combination of SOCl2, benzotriazole, and potassium halides in DMF is described. The effectiveness of the protocol is manifested in its selectivity towards allylic and benzylic alcohols whereas other simple alcohols such as primary, secondary, and tertiary are found to be unreactive. Springer-Verlag 2004.
- Bandgar, Babasaheb P.,Bettigeri, Sampada V.
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p. 1251 - 1255
(2007/10/03)
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- A convenient synthesis of trifluoromethyl ethers by oxidative desulfurization-fluorination of dithiocarbonates
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Trifluoromethyl ethers R-OCF3 are easily synthesized from the corresponding dithiocarbonates R-OCS2Me (R = aryl or primary alkyl) by a reagent system consisting of 70% HF/pyridine and an N-halo imide. When the reaction is applied to R-OCS2Me wherein R = secondary alkyl, tertiary alkyl, or benzylic group, fluorination leading to the corresponding alkyl fluorides R-F is achieved, whereas a combination of 50% HF/pyridine and N- bromosuccinimide affords the corresponding trifluoromethyl ethers R-OCF3 (R = secondary).
- Kanie, Kiyoshi,Tanaka, Yoichiro,Suzuki, Kazundo,Kuroboshi, Manabu,Hiyama, Tamejiro
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p. 471 - 484
(2007/10/03)
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- Oxidative desulfurization-fluorination of alkanol xanthates. Control of the reaction pathway to fluorination or trifluoromethoxylation
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The reagent consisting of 70% HF-py (py = pyridine) and a halonium oxidant converts R-OCS2Me into either R-OCF3 (R = primary) or R-F (R = secondary, tertiary or benzylic) whereas the 50% HF-py system converts R-OCS2Me (R =
- Kanie, Kiyoshi,Tanaka, Yoichiro,Shimizu, Masaki,Kuroboshi, Manabu,Hiyama, Tamejiro
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p. 309 - 310
(2007/10/03)
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- FLUORINATION OF HALOGENO ALCOHOLS WITH 1,1,2,3,3,3-HEXAFLUOROPROPYL DIETHYLAMINE
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Fluorination of halogeno alcohols with 1,1,2,3,3,3-hexafluoropropyl diethylamine (PPDA) was investigated. 2-Bromo-1-fluorobutane was obtained from the reaction of PPDA and 2-bromo-1-butanol (yield 50percent).Similar results were obtained from other alipha
- Watanabe, S.,Fujita, T.,Usui, Y.,Kimura, Y.
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p. 135 - 142
(2007/10/02)
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