433-98-7Relevant academic research and scientific papers
Molecular structure and conformations of 2-nitrobenzenesulfonyl fluoride: Gas-phase electron diffraction and quantum chemical calculations study
Petrov, Vjacheslav M.,Girichev, Georgiy V.,Oberhammer, Heinz,Giricheva, Nina I.,Bardina, Anna V.,Petrova, Valentina N.,Ivanov, Sergey N.
, p. 97 - 103 (2010)
The molecular structure and conformational properties of 2-nitrobenzenesulfonyl fluoride, 2-NO2-C6H4SO2F, have been studied by gas-phase electron diffraction (GED) and quantum chemical methods (B3LYP/6-311+G and MP2/6-31G). Quantum chemical calculations predict the existence of three conformers for 2-NO2-C6H4SO2F each of them possesses C1 symmetry. Conformer I, in which the S-F bond of the SO2F group is nearly perpendicular to the plane of benzene ring, is predicted to be most favored. Conformer II, in which the S-F bond is situated in opposite direction with reference to the NO2 group, possesses intermediate energy (Δ1-2 = 0.73 kcal/mol (B3LYP), or 0.71 kcal/mol (MP2)), and conformer III with the S-F bond tilted to the NO2 group possesses the higher energy (Δ1-3 = 1.58 kcal/mol (B3LYP), or 1.47 kcal/mol (MP2)). The analysis of the GED intensities was carried out assuming the vapour consists of three conformers. In was obtained the conformer I dominates in vapour over solid 2-NO2-C6H4SO2F at T = 383(5) K. The conformer III concentration was found to be negligible. In dominant conformer I the S-F bond is bent slightly towards the nitro group (φ(C-C-S-F) = 84(8)°), and the torsional angle of the nitro group with respect to the benzene ring φ(C-C-N-O) equals 125(4)°. The conformation properties were determined by the potential energy surface analysis. The relative stability of conformers is discussed.
Metal-Free Visible-Light Synthesis of Arylsulfonyl Fluorides: Scope and Mechanism
Louvel, Dan,Chelagha, Aida,Rouillon, Jean,Payard, Pierre-Adrien,Khrouz, Lhoussain,Monnereau, Cyrille,Tlili, Anis
, p. 8704 - 8708 (2021/05/17)
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.
Synthesis of Sulfonyl Fluorides from Sulfonamides
Pérez-Palau, Marina,Cornella, Josep
supporting information, p. 2497 - 2500 (2020/03/11)
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.
SuFEx-enabled, agnostic discovery of covalent inhibitors of human neutrophil elastase
Zheng, Qinheng,Woehl, Jordan L.,Kitamura, Seiya,Santos-Martins, Diogo,Smedley, Christopher J.,Li, Gencheng,Forli, Stefano,Moses, John E.,Wolan, Dennis W.,Barry Sharpless
, p. 18808 - 18814 (2019/09/30)
Sulfur fluoride exchange (SuFEx) has emerged as the new generation of click chemistry. We report here a SuFEx-enabled, agnostic approach for the discovery and optimization of covalent inhibitors of human neutrophil elastase (hNE). Evaluation of our ever-growing collection of SuFExable compounds toward various biological assays unexpectedly revealed a selective and covalent hNE inhibitor: benzene-1,2-disulfonyl fluoride. Synthetic derivatization of the initial hit led to a more potent agent, 2-(fluorosulfonyl)phenyl fluorosulfate with IC50 0.24 μM and greater than 833-fold selectivity over the homologous neutrophil serine protease, cathepsin G. The optimized, yet simple benzenoid probe only modified active hNE and not its denatured form.
(Chlorosulfonyl)benzenesulfonyl Fluorides - Versatile Building Blocks for Combinatorial Chemistry: Design, Synthesis and Evaluation of a Covalent Inhibitor Library
Tolmachova, Kateryna A.,Moroz, Yurii S.,Konovets, Angelika,Platonov, Maxim O.,Vasylchenko, Oleksandr V.,Borysko, Petro,Zozulya, Sergey,Gryniukova, Anastasia,Bogolubsky, Andrey V.,Pipko, Sergey,Mykhailiuk, Pavel K.,Brovarets, Volodymyr S.,Grygorenko, Oleksandr O.
, p. 672 - 680 (2018/11/23)
Multigram synthesis of (chlorosulfonyl)benzenesulfonyl fluorides is described. Selective modification of these building blocks at the sulfonyl chloride function under parallel synthesis conditions is achieved. It is shown that the reaction scope includes the use of (hetero)aromatic and electron-poor aliphatic amines (e.g., amino nitriles). Utility of the method is demonstrated by preparation of the sulfonyl fluoride library for potential use as covalent fragments, which is demonstrated by a combination of in silico and in vitro screening against trypsin as a model enzyme. As a result, several inhibitors were identified with activity on par with that of the known inhibitor.
Sulfur(VI) fluoride compounds and methods for the preparation thereof
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Page/Page column 19; 20; 36; 45; 46, (2018/11/23)
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.
A study of the reactivity of S(VI)-F containing warheads with nucleophilic amino-acid side chains under physiological conditions
Mukherjee,Debreczeni,Breed,Tentarelli,Aquila,Dowling,Whitty,Grimster
supporting information, p. 9685 - 9695 (2017/11/30)
Sulfonyl fluorides (SFs) have recently emerged as a promising warhead for the targeted covalent modification of proteins. Despite numerous examples of the successful deployment of SFs as covalent probe compounds, a detailed exploration of the factors influencing the stability and reactivity of SFs has not yet appeared. In this work we present an extensive study on the influence of steric and electronic factors on the reactivity and stability of the SF and related SVI-F groups. While SFs react rapidly with N-acetylcysteine, the resulting adducts were found to be unstable, rendering SFs inappropriate for the durable covalent inhibition of cysteine residues. In contrast, SFs afforded stable adducts with both N-acetyltyrosine and N-acetyllysine; furthermore, we show that the reactivity of arylsulfonyl fluorides towards these nucleophilic amino acids can be predictably modulated by adjusting the electronic properties of the warhead. These trends were largely conserved when the covalent reaction occurred within a protein binding pocket. We have also obtained a crystal structure depicting covalent modification of the catalytic lysine of a tyrosine kinase (FGFR1) by the ATP analog 5′-O-3-((fluorosulfonyl)benzoyl)adenosine (m-FSBA). Highly reactive warheads were demonstrated to be unstable with respect to hydrolysis in buffered aqueous solutions, indicating that warhead reactivity must be carefully tuned to provide optimal rates of protein modification. Our results demonstrate that the reactivity of SFs complements that of more commonly studied acrylamides, and we hope that this work spurs the rational design of novel SF-containing covalent probe compounds and inhibitors, particularly in cases where a suitably positioned cysteine residue is not present.
Catalyst-free radical fluorination of sulfonyl hydrazides in water
Tang, Lin,Yang,Wen, Lixian,Yang, Xingkun,Wang, Zhiyong
, p. 1224 - 1228 (2016/03/09)
The first catalyst-free fluorination of sulfonyl hydrazides for the synthesis of sulfonyl fluorides has been developed via a free-radical pathway. This protocol presents a broad substrate scope and does not require any metal catalyst and additive. All these transformations proceed smoothly in water under mild conditions, which enables a straightforward, practical and environmentally benign fluorination for S-F bond formation.
KINETIC INVESTIGATION OF THE S-FLUORINATION OF ARENESULFINATES WITH PERCHLORYL FLUORIDE
Vigalok, I. V.,Petrova, G. G.,Lukashina, S. G.,Vigalok, A. A.,Levin, Ya. A.
, p. 1239 - 1243 (2007/10/02)
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.
