- Copper-catalyzed three-component reaction of arylhydrazine hydrochloride, DABSO, and NFSI for the synthesis of arenesulfonyl fluorides
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This paper reports a convenient copper-catalyzed three-component conversion of arylhydrazine hydrochlorides to arenesulfonyl fluorides in good yields under mild conditions, using 1,4-diazabicyclo [2.2.2]octane bis(sulfur dioxide) (DABSO) as a sulfonyl source andN-fluorobenzenesulfonimide (NFSI) as a fluorine source based on a radical sulfur dioxide insertion and fluorination strategy. Notably, arylhydrazine hydrochloride is used as a safe precursor of aryl radicals.
- Chen, Qing-Yun,Guo, Yong,Hu, Xiaojun,Liu, Chao,Liu, Yongan,Ma, Xiaoyu,Pan, Qijun,Pang, Wan,Wu, Jingjing
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supporting information
p. 8999 - 9003
(2021/11/04)
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- Method for preparing aryl sulfonyl fluoride by using aryl hydrazine hydrochloride as raw material
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The invention relates to a method for preparing aryl sulfonyl fluoride by using aryl hydrazine hydrochloride as a raw material. According to the method, aryl sulfonyl fluoride is synthesized by taking the aryl hydrazine hydrochloride as a raw material and adding a sulfur dioxide source and a fluorination reagent under the conditions of copper salt catalysis and alkali promotion through a strategy of insertion and fluorination of free radical sulfur dioxide. Compared with the prior art, the aryl sulfonyl fluoride is synthesized under the oxidation condition, and the influence of air on the reaction is not obvious in an experiment; and the reaction synthesis method is simple, good in selectivity, excellent in yield, mild in reaction condition, short in reaction time and universal to various aryl hydrazine hydrochloride substrates, and the method provides a new thought for synthesis of aryl sulfonyl fluoride.
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Paragraph 0048-0077
(2021/11/06)
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- Metal-Free Visible-Light Synthesis of Arylsulfonyl Fluorides: Scope and Mechanism
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The first metal-free procedure for the synthesis of arylsulfonyl fluorides is reported. Under organo-photoredox conditions, aryl diazonium salts react with a readily available SO2 source (DABSO) to afford the desired product through simple nucleophilic fluorination. The reaction tolerates the presence of both electron-rich and -poor aryls and demonstrated a broad functional group tolerance. To shed the light on the reaction mechanism, several experimental techniques were combined, including fluorescence, NMR, and EPR spectroscopy as well as DFT calculations.
- Louvel, Dan,Chelagha, Aida,Rouillon, Jean,Payard, Pierre-Adrien,Khrouz, Lhoussain,Monnereau, Cyrille,Tlili, Anis
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supporting information
p. 8704 - 8708
(2021/05/17)
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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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- Synthesis of Sulfonyl Fluorides from Sulfonamides
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A simple and practical synthesis of sulfonyl fluorides from sulfonamides is reported. The method capitalizes on the formation of the sulfonyl chloride by virtue of the reaction of Pyry-BF4 and MgCl2, and subsequent in situ conversion to the more robust and stable sulfonyl fluoride by the presence of KF. The mild conditions and high chemoselectivity of the protocol enable the late-stage formation of sulfonyl fluorides from densely functionalized molecules.
- Pérez-Palau, Marina,Cornella, Josep
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supporting information
p. 2497 - 2500
(2020/03/11)
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- A Unified Strategy for Arylsulfur(VI) Fluorides from Aryl Halides: Access to Ar-SOF3 Compounds
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A convenient protocol to selectively access various arylsulfur(VI) fluorides from commercially available aryl halides in a divergent fashion is presented. Firstly, a novel sulfenylation reaction with the electrophilic N-(chlorothio)phthalimide (Cl-S-Phth) and arylzinc reagents afforded the corresponding Ar-S-Phth compounds. Subsequently, the S(II) atom was selectively oxidized to distinct fluorinated sulfur(VI) compounds under mild conditions. Slight modifications on the oxidation protocol permit the chemoselective installation of 1, 3, or 4 fluorine atoms at the S(VI) center, affording the corresponding Ar-SO2F, Ar-SOF3, and Ar-SF4Cl. Of notice, this strategy enables the effective introduction of the rare and underexplored -SOF3 moiety into various (hetero)aryl groups. Reactivity studies demonstrate that such elusive Ar-SOF3 can be utilized as a linchpin for the synthesis of highly coveted aryl sulfonimidoyl fluorides (Ar-SO(NR)F).
- Cornella, Josep,Wang, Lin
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supporting information
p. 23510 - 23515
(2020/10/29)
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- Arenesulfonyl Fluoride Synthesis via Copper-free Sandmeyer-type Fluorosulfonylation of Arenediazonium Salts
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The limited availability of highly valuable arenesulfonyl fluorides seriously hinders their further application in many research fields including medicinal chemistry and chemical biological, organic synthesis, polymer preparation, etc. We report herein a mild and efficient copper-free Sandmeyer-type fluorosulfonylation reaction of various arenediazonium salts to prepare valuable arenesulfonyl fluorides using K2S2O5 as both a reductant and a practical sulfonyl source in combination with N-fluorobenzenesulfonimide as an effective fluorine source. This methodology provides an attractive route to diverse important arenesulfonyl fluorides given the overall practicality and scope.
- Lin, Qiongzhen,Ma, Zhanhu,Zheng, Changge,Hu, Xiao-Jun,Guo, Yong,Chen, Qing-Yun,Liu, Chao
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supporting information
p. 1107 - 1110
(2020/07/06)
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- Arylsulfonyl fluoride boronic acids: Preparation and coupling reactivity
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We report the efficient and practical syntheses of ortho-, meta, and para-sulfonyl fluoride substituted benzene boronic acids. The syntheses of the para- and meta-isomers commence with the appropriate bromo-substituted benzenesulfonyl chlorides, and the o
- Lou, Terry Shing-Bong,Willis, Michael C.
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- Sulfonyl Fluoride Synthesis through Electrochemical Oxidative Coupling of Thiols and Potassium Fluoride
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Sulfonyl fluorides are valuable synthetic motifs for a variety of applications, among which sulfur(VI) fluoride exchange-based "click chemistry" is currently the most prominent. Consequently, the development of novel and efficient synthetic methods to access these functional groups is of great interest. Herein, we report a mild and environmentally benign electrochemical approach to prepare sulfonyl fluorides using thiols or disulfides, as widely available starting materials, in combination with KF, as an inexpensive, abundant and safe fluoride source. No additional oxidants nor additional catalysts are required and, due to mild reaction conditions, the reaction displays a broad substrate scope, including a variety of alkyl, benzyl, aryl and heteroaryl thiols or disulfides.
- Laudadio, Gabriele,Bartolomeu, Aloisio De A.,Verwijlen, Lucas M. H. M.,Cao, Yiran,De Oliveira, Kleber T.,No?l, Timothy
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supporting information
p. 11832 - 11836
(2019/08/26)
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- Copper-Catalyzed Synthesis of Activated Sulfonate Esters from Boronic Acids, DABSO, and Pentafluorophenol
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The synthesis of pentafluorophenyl (PFP) sulfonate esters based on the Pd-catalyzed sulfination of aryl and heteroaryl boronic acids is reported. The sulfinate intermediates are converted in situ to the corresponding sulfonate esters using a copper-catalyzed oxidative process, providing a broad range of PFP esters in good yields.
- Vedovato, Vincent,Talbot, Eric P. A.,Willis, Michael C.
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p. 5493 - 5496
(2018/09/12)
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- Sulfur(VI) fluoride compounds and methods for the preparation thereof
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This application describes a compound represented by Formula (I): (I) wherein: Y is a biologically active organic core group comprising one or more of an aryl group, a heteroaryl aryl group, a nonaromatic hydrocarbyl group, and a nonaromatic heterocyclic group, to which Z is covalently bonded; n is 1, 2, 3, 4 or 5; m is 1 or 2; Z is O, NR, or N; X1 is a covalent bond or —CH2CH2—, X2 is O or NR; and R comprises H or a substituted or unsubstituted group selected from an aryl group, a heteroaryl aryl group, a nonaromatic hydrocarbyl group, and a nonaromatic heterocyclic group. Methods of preparing the compounds, methods of using the compounds, and pharmaceutical compositions comprising the compounds are described as well.
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Page/Page column 19; 20; 36; 45
(2018/11/23)
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- NEW ANTIFIBRINOLYTIC COMPOUNDS
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It relates to spirocyclic compounds of formula (I),or pharmaceutically or veterinary acceptable salts thereof, or any stereoisomers either of the compounds of formula (I) or of their pharmaceutically or veterinary acceptable salts, wherein A and B form a spirocyclic ring system wherein the spiro atom connecting A and B is a carbonatom and wherein A is a known 3- to 8-membered carbocyclic or heterocyclic monocyclic ring or a known 6- to 18-membered carbocyclic or heterocyclic polycyclic ring system; B is a known 4- to 7-membered carbocyclic or heterocyclic monocyclic ring; C is phenyl or a known 5- to 6-membered heteroaromatic ring; and R1-R7 are as defined herein. It also relates to a process for their preparation, as well as to the intermediates used in this process; to pharmaceutical or veterinary compositions containing them, and to their use in medicine, in particular as antifibrinolytic and antihemorragic agents.
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Page/Page column 49
(2014/02/15)
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- Ascertaining the suitability of aryl sulfonyl fluorides for [18F]radiochemistry applications: A systematic investigation using microfluidics
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Optimization of [18F]radiolabeling conditions and subsequent stability analysis in mobile phase, PBS buffer, and rat serum of 12 aryl sulfonyl chloride precursors with various substituents (electron-withdrawing groups, electron-donating groups, increased steric bulk, heterocyclic) were performed using an Advion NanoTek Microfluidic Synthesis System. A comparison of radiochemical yields and reaction times for a microfluidics device versus a conventional reaction vessel is reported. [18F]Radiolabeling of sulfonyl chlorides in the presence of competing nucleophiles, H-bond donors, and water was also assessed and demonstrated the versatility and potential utility of [18F]sulfonyl fluorides as synthons for indirect radiolabeling. Published 2013 by the American Chemical Society.
- Matesic, Lidia,Wyatt, Naomi A.,Fraser, Benjamin H.,Roberts, Maxine P.,Pham, Tien Q.,Greguric, Ivan
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p. 11262 - 11270
(2013/12/04)
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- The investigation of fluorination reaction of p-substituted benzenesulfonimides with fluorine-nitrogen mixed gas to synthesize NFSI analogues
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This paper studied the fluorination reaction of p-substituted benzenesulfonimides with diluted elemental fluorine to synthesize N-fluoro-benzenesulfonimide (NFSI) analogues. Several synthetic methods were compared and we found that, for many p-substituted
- Yang, Xianjin,Chen, Guanlong,Chen, Fuli,Zhang, Yan,Yang, Xueyan,Yuan, Xiaoming,Wu, Fanhong
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scheme or table
p. 155 - 159
(2012/02/14)
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- A convenient, one-pot procedure for the preparation of acyl and sulfonyl fluorides using Cl3CCN, Ph3P, and TBAF(t -BuOH) 4
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Various carboxylic acids were converted into acyl fluorides in excellent yields by treatment with trichloroacetonitrile, triphenylphosphine, and TBAF(t-BuOH)4 at room temperature. The reaction was applicable to the preparation of acid-sensitive amino acid fluorides without deprotection or rearrangement
- Kim, Joong-Gon,Jang, Doo Ok
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experimental part
p. 3049 - 3052
(2011/02/25)
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- Substituted nipecotyl derivatives as inhibitors of cell adhesion
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Compounds of Formula I are antagonists of VLA-4 and/or α4β7, and as such are useful in the inhibition or prevention of cell adhesion and cell-adhesion mediated pathologies. These compounds may be formulated into pharmaceutical compos
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- The Combination of Potassium Fluoride and Calcium Fluoride: A Useful Heterogeneous Fluorinating Reagent
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The combination of potassium fluoride and calcium fluoride was found to be an effective and practical solid reagent for the fluorination of various organic chlorides and bromides under mild conditions.
- Ichihara, Junko,Matsuo, Toshiya,Hanafusa, Terukiyo,Ando, Takashi
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p. 793 - 794
(2007/10/02)
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- KINETIC INVESTIGATION OF THE S-FLUORINATION OF ARENESULFINATES WITH PERCHLORYL FLUORIDE
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The effect of substituents and solvents on the kinetics of S-fluorination of sodium arenesulfinates with perchloryl fluoride was investigated.Alternative fluorination mechanisms were examined, and it was found that the mechanism is SN2 substitution at the fluorine atom.
- Vigalok, I. V.,Petrova, G. G.,Lukashina, S. G.,Vigalok, A. A.,Levin, Ya. A.
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p. 1239 - 1243
(2007/10/02)
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