- 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; 0184-0187; 0188
(2021/04/10)
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- Base-Catalyzed H/D Exchange Reaction of Difluoromethylarenes
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The budding deuteriodifluoromethyl group (CF2D) is a potentially significant functional group in medicinal chemistry. Herein, we investigated t-BuOK-catalyzed H/D exchange reaction of difluoromethylarenes in DMSO-d6 solution. The method provides excellent
- Huang, Linwei,Liu, Wei,Zhao, Liang-Liang,Zhang, Zengyu,Yan, Xiaoyu
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p. 3981 - 3988
(2021/03/09)
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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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- Deoxyfluorination of (Hetero)aryl Aldehydes Using Tetramethylammonium Fluoride and Perfluorobutanesulfonyl Fluoride or Trifluoromethanesulfonic Anhydride
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This Communication describes the conversion of (hetero)aryl aldehydes into the corresponding (hetero)aryl difluoromethyl products using anhydrous NMe4F in combination with perfluorobutanesulfonyl fluoride or trifluoromethanesulfonic anhydride.
- Ferguson, Devin M.,Melvin, Patrick R.,Sanford, Melanie S.
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p. 398 - 401
(2019/09/06)
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- Room Temperature Deoxyfluorination of Benzaldehydes and α-Ketoesters with Sulfuryl Fluoride and Tetramethylammonium Fluoride
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A method for the room temperature deoxyfluorination of benzaldehydes and α-ketoesters using sulfuryl fluoride and Me4NF is described. A large scope of aryl and heteroaryl substrates is demonstrated, and this method compares favorably to other common deoxyfluorination methods for many substrates.
- Melvin, Patrick R.,Ferguson, Devin M.,Schimler, Sydonie D.,Bland, Douglas C.,Sanford, Melanie S.
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supporting information
p. 1350 - 1353
(2019/03/08)
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- Nickel-Catalyzed Aromatic Cross-Coupling Difluoromethylation of Grignard Reagents with Difluoroiodomethane
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The nickel-catalyzed cross-coupling difluoromethylation of the Grignard reagents with difluoroiodomethane is shown to provide the corresponding aromatic difluoromethyl products in excellent to moderate yields. The difluoromethylation proceeds smoothly within 1 h at room temperature with 1.5 equiv of the Grignard reagents in the presence of Ni(cod)2/TMEDA (2.5-0.5 mol %). Mechanistic studies clarify that the oxidative addition of the Ni(0) catalyst to difluoroiodomethane provides the TMEDA-Ni(II)(CF2H)I complex. This intermediate is transformed to TMEDA-Ni(II)(CF2H)Ph via transmetalation with PhMgBr. The reductive elimination takes place to give the aromatic cross-coupling difluoromethylation product along with regeneration of the TMEDA-Ni(0) catalyst. Electron paramagnetic resonance (EPR) and radical clock analyses of the nickel-catalyzed reaction provide no EPR active Ni(I) and Ni(III) species at around g = 2 and only a trace amount of the cyclization product.
- Motohashi, Hirotaka,Mikami, Koichi
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supporting information
p. 5340 - 5343
(2018/09/12)
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- PIPERAZINE DERIVATIVES AS TRPML MODULATORS
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The new piperazine derivatives are modulators of TRPML and are useful in treating disorders related to TRPML activities such as lysosome storage diseases, muscular dystrophy, age-related common neurodegenerative diseases, oxidative stress or reactive oxygen species (ROS) related diseases, and ageing.
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Page/Page column 43; 44
(2018/02/03)
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- Synthesis of Aryldihalomethanes by Denitrogenative Dihalogenation of Benzaldehyde Hydrazones
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We report a denitrogenative dihalogenation reaction of phenyldiazomethanes in which the hypervalent iodine reagents PhICl2 and TolIF2 act as surrogates for elemental chlorine and fluorine. Halogen transfer from iodane to aryldiazomethane is described, as is a tandem oxidative dihalogenation reaction between iodane and hydrazone. This is the first use of non-α-stabilized diazo compounds in this reaction, which provided an efficient synthesis of aryldifluoromethane (ArCHF2) and aryldichloromethane (ArCHCl2) derivatives. (Figure presented.).
- Zhao, Zhensheng,Kulkarni, Kaivalya G.,Murphy, Graham K.
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supporting information
p. 2222 - 2228
(2017/07/07)
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- Synthesis of trifluoromethyl moieties by late-stage copper (I) mediated nucleophilic fluorination
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The nucleophilic fluorination of bromodifluoromethyl derivatives mediated by the complex (PPh3)3CuF is described. Under the reaction conditions, different trifluoroacetates, trifluoroketones, trifluoroarenes and trifluoroacetamides were obtained in good yields.
- Bermejo Góme, Antonio,González, Miguel A. Cortés,Lübcke, Marvin,Johansson, Magnus J.,Schou, Magnus,Szabó, Kálmán J.
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- Pd-Catalyzed Transfer of Difluorocarbene
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The study of transition-metal difluorocarbene complex has long been a subject of active investigation, but the transition-metal-catalyzed transfer of difluorocarbene remains a significant challenge. The Pd-catalyzed transfer of difluorocarbene is described to realize the coupling reaction of boronic acids with difluorocarbene to give (difluoromethyl)arenes and -olefins. Mechanistic investigations reveal that the Pd? -CF2 complex is an important intermediate for this transformation. This complex is prone to trimerization without the presence of starting materials.
- Deng, Xiao-Yun,Lin, Jin-Hong,Xiao, Ji-Chang
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supporting information
p. 4384 - 4387
(2016/11/01)
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- Transition-metal-free C-H oxidative activation: Persulfate-promoted selective benzylic mono- and difluorination
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An operationally simple and selective method for the direct conversion of benzylic C-H to C-F to obtain mono- and difluoromethylated arenes using Selectfluor as a fluorine source is developed. Persulfate can be used to selectively activate benzylic hydrogen atoms toward C-F bond formation without the aid of transition metal catalysts.
- Ma, Jing-Jing,Yi, Wen-Bin,Lu, Guo-Ping,Cai, Chun
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supporting information
p. 2890 - 2894
(2015/04/27)
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- Well-Defined, Shelf-Stable (NHC)Ag(CF2H) Complexes for Difluoromethylation
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The preparation of the thermally stable, well-defined NHC-ligated difluoromethylated silver complexes 1a,b is described. The complexes were fully characterized, and the structural assignments were ambiguously further confirmed by single-crystal X-ray diffraction. Reactions of [(SIPr)Ag(CF2H)] with a variety of activated electrophiles such as diaryliodonium salts, vinyl(aryl)iodonium salts, aryldiazonium salts, and acid chlorides in the presence or absence of CuI occurred smoothly at room temperature to generate difluoromethylated compounds in good to excellent yields. (Chemical Equation Presented).
- Gu, Yang,Chang, Dalu,Leng, Xuebing,Gu, Yucheng,Shen, Qilong
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supporting information
p. 3065 - 3071
(2015/06/30)
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- Method of manufacturing arom. defluoromethyl compd.
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PROBLEM TO BE SOLVED: To provide a method for easily producing an aromatic compound having a difluoromethyl group in high yield while using a reagent having low toxicity. SOLUTION: The method for producing the aromatic difluoromethyl compound includes reacting an aromatic difluoroacetic acid in the presence of a metal halide (especially potassium fluoride). COPYRIGHT: (C)2011,JPOandINPIT
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Paragraph 0080; 0086
(2018/11/22)
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- ARYLAMINOPYRAZOLE DERIVATIVE
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PROBLEM TO BE SOLVED: To provide a compound represented by formula (1) or a pharmacologically acceptable salt thereof. SOLUTION: The compound represented by the formula (1) or the pharmacologically acceptable salt thereof is provided. [In the formula, Rs
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Paragraph 0204-0207
(2020/04/21)
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- Catalytic decarboxylative fluorination for the synthesis of Tri- and difluoromethyl arenes
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Treatment of readily available α,α-difluoro- and α-fluoroarylacetic acids with Selectfluor under Ag(I) catalysis led to decarboxylative fluorination. This operationally simple reaction gave access to tri- and difluoromethylarenes applying a late-stage fluorination strategy. Translation to [18F]labeling is demonstrated using [ 18F]Selectfluor bis(triflate), a reagent affording [ 18F]tri- and [18F]difluoromethylarenes not within reach with [18F]F2.
- Mizuta, Satoshi,Stenhagen, Ida S.R.,O'Duill, Miriam,Wolstenhulme, Jamie,Kirjavainen, Anna K.,Forsback, Sarita J.,Tredwell, Matthew,Sandford, Graham,Moore, Peter R.,Huiban, Mickael,Luthra, Sajinder K.,Passchier, Jan,Solin, Olof,Gouverneur, Véronique
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supporting information
p. 2648 - 2651
(2013/07/11)
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- Copper-mediated difluoromethylation of (hetero)aryl iodides and β-styryl halides with tributyl(difluoromethyl)stannane
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Owing to their unique properties, molecules containing the difluoromethyl group (CF2H) are of great interest. Tributyl(difluoromethyl)stannane has now been used for the selective and efficient direct ipso difluoromethylation of aryl iodides, he
- Prakash, G. K. Surya,Ganesh, Somesh K.,Jones, John-Paul,Kulkarni, Aditya,Masood, Kamil,Swabeck, Joseph K.,Olah, George A.
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p. 12090 - 12094
(2013/01/16)
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- Method of Synthesis of Arylsulfur Trifluorides and Use as in situ Deoxofluorination Reagent
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The invention is a method of synthesizing Arylsulfur Trifluorides, such as Fluolead, by reacting BR2 and KF (or suitable alkali metal fluoride) in acetonitrile (or other suitable solvent). The invention also comprises using the Fluolead (or its
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Page/Page column 2; 3
(2012/04/11)
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- Imidazo[5,1-f][1,2,4]Triazines for the Treatment of Neurological Disorders
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The present invention relates to compounds of the Formula and pharmaceutically acceptable salts thereof, to processes for the preparation of, intermediates used in the preparation of, and compositions containing such compounds and the uses of such compounds as a method for the treatment of a disease or condition selected from the group consisting of central nervous system disorders, cognitive disorders, schizophrenia, dementia and other disorders in a mammal.
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Page/Page column 27
(2012/09/05)
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- A new method for aromatic difluoromethylation: Copper-catalyzed cross-coupling and decarboxylation sequence from aryl iodides
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A new methodology for aromatic difluoromethylation is described. Aryl iodides reacted with α-silyldifluoroacetates upon treatment with copper catalyst in DMSO or DME to give the corresponding aryldifluoroacetates in moderate to good yields. The subsequent hydrolysis of aryldifluoroacetates and KF-promoted decarboxylation afforded a variety of difluoromethyl aromatics.
- Fujikawa, Kenichi,Fujioka, Yasutaka,Kobayashi, Akira,Amii, Hideki
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p. 5560 - 5563
(2011/12/05)
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- Arylsulfur trifluorides: Improved method of synthesis and use as in situ deoxofluorination reagents
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Building on recent results of Umemoto and Winter, an improved method of synthesis of arylsulfur trifluorides, including the excellent, new deoxofluorination reagent Fluolead, is hereby reported. The method utilizes Br2 and KF as oxidizing and fluorinating reagents for efficient, high yield conversion of aryl disulfides and mercaptans to arylsulfur trifluorides. It has also been shown that both Fluolead and mesitylsulfur trifluoride may be generated in acetonitrile and used as in situ deoxofluorination reagents for conversion of either aldehydes or ketones to their respective gem-difluoro compounds. An analysis of the probable mechanism of action, including computational efforts, allows postulation of a rationale for the highly variable reactivities of different arylsulfur trifluorides as deoxofluorination reagents.
- Xu, Wei,Martinez, Henry,Dolbier Jr., William R.
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experimental part
p. 482 - 488
(2011/08/03)
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