- Selective synthesis of sulfoxides and sulfonesviacontrollable oxidation of sulfides withN-fluorobenzenesulfonimide
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A practical and mild method for the switchable synthesis of sulfoxides or sulfonesviaselective oxidation of sulfides using cheapN-fluorobenzenesulfonimide (NFSI) as the oxidant has been developed. These highly chemoselective transformations were simply achieved by varying the NFSI loading with H2O as the green solvent and oxygen source without any additives. The good functional group tolerance makes the strategy valuable.
- Cao, Zhong-Yan,Li, Xiaolong,Lu, Hao,Wang, Panpan,Wang, Shengqiang,Xu, Xiaobo,Yan, Leyu,Yang, A-Xiu
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supporting information
p. 8691 - 8695
(2021/10/22)
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- An efficient heterogeneous copper fluorapatite (CuFAP)-catalysed oxidative synthesis of diaryl sulfone under mild ligand- and base-free conditions
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A simple, eco-friendly and efficient method for the synthesis of unsymmetrical diaryl sulfones using heterogeneous copper fluorapatite (CuFAP)-catalysed coupling of aryl sulfonic acid and phenyl boronic acid has been developed with good to excellent yields without use of any ligand, base or co-catalyst. Broad substrate scope and gram scale operations are the important features of this method.
- Kamble, Rohit B.,Chavan, Santosh S.,Suryavanshi, Gurunath
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p. 1632 - 1636
(2019/01/21)
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- Silver-promoted decarboxylative sulfonylation of aromatic carboxylic acids with sodium sulfinates
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A novel and efficient synthesis of sulfones was developed via a silver-promoted decarboxylative sulfonylation reaction between aromatic carboxylic acids and sodium sulfinates for the first time. The approach features operational simplicity and good functional group compatibility and uses readily available starting materials. Furthermore, mechanistic studies reveal that the decarboxylative sulfonylation reaction is likely to proceed via a radical mechanism.
- Yu, Yongqi,Wu, Qianlong,Liu, Da,Yu, Lin,Tan, Ze,Zhu, Gangguo
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p. 11195 - 11202
(2019/09/12)
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- Carbon-supported metal-modified lacunary tungstosilicic polyoxometallates used as catalysts in the selective oxidation of sulfides
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Lacunary tungstosilicic polyoxometallates modified with transition metal ions [SiW11O39M(H2O)]6-, where M = Mn2+, Fe2+, Co2+or Cu2+, were synthesized and supported on activated carbon to obtain the SiW11MC catalysts. The samples were characterized by FT-IR, XRD, N2 adsorption-desorption measurements, and the acidic properties were determined using the isopropanol dehydration test reaction. The activity and selectivity of the catalysts were evaluated in the selective oxidation of a series of sulfides to sulfoxides or sulfone. The reaction was carried out in acetonitrile as solvent using H2O2 35% p/V as a clean oxidant. The conversion values decreased in the following order: SiW11MnC > SiW11FeC > SiW11CuC > SiW11CoC. The catalysts were reused without appreciable loss of their catalytic activity. It was found that the activity of the catalysts decreases in parallel with the increment in the reduction temperature values. The most easily reducible catalyst displayed the highest conversion values. We found a convenient and selective procedure for oxidizing sulfides to sulfoxides or sulfones using aqueous hydrogen peroxide and a catalytic amount of lacunary tungstosilicic polyoxometallates supported on carbon at low temperatures (20-50 °C) in a reasonably short reaction time
- Frenzel, Romina,Sathicq, ángel G.,Blanco, Mirta N.,Romanelli, Gustavo P.,Pizzio, Luis R.
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- Synthesis and biological evaluation of optimized inhibitors of the mitotic kinesin Kif18A
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The mitotic spindle, a highly dynamic structure composed of microtubules, mediates the segregation of the previously duplicated genome into the two nascent daughter cells. Errors in this process contribute to pathology including tumor formation. Key for the shape and function of the mitotic spindle are kinesins, molecular motor proteins that convert chemical energy into mechanical work. Due to their fast mode of action, small molecules are valuable tools to dissect the dynamic functions of kinesins during mitosis. In this study, we report the identification of optimized small molecule inhibitors of the mitotic kinesin Kif18A. Using BTB-1, the first identified Kif18A inhibitor, as a lead compound, we synthesized a collection of derivatives. We demonstrate that some of the synthesized derivatives potently inhibited the ATPase activity of Kif18A with a half maximal inhibitory concentration (IC50) value in the low micromolar range. In vitro analysis of a panel of Kif18A-related kinesins revealed that the two most potent compounds show improved selectivity compared to BTB-1. Structure-activity relationship studies identified substituents mediating undesired inhibitory effects on microtubule polymerization. In summary, our study provides key insights into the mechanism of action of BTB-1 and its analogs, which will have a great impact on the further development of highly selective and bioactive Kif18A inhibitors. Since Kif18A is frequently overexpressed in solid tumors, such compounds are not only of great interest for basic research but also have the potential to open up new strategies for the treatment of human diseases.
- Braun, Joachim,M?ckel, Martin M.,Strittmatter, Tobias,Marx, Andreas,Groth, Ulrich,Mayer, Thomas U.
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p. 554 - 560
(2015/04/21)
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- Synthesis of substituted diphenyl sulfones and their structure-activity relationship with the antagonism of 5-HT6 receptors
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Substituted diphenyl sulfones (10a-n) were synthesised, and the structures were confirmed by NMR, LC-MS and X-ray crystallography. Their antagonistic activities towards 5-HT6 receptor were assessed in a cell-based functional assay. Diphenyl sulfone 10a, in spite of being the smallest and simplest known sulfonyl-containing 5-HT6R antagonist, showed a strong potency (Ki = 1.6 μM). Its derivative with a methylamine substituent, 10g (N-methyl-2-(phenylsulfonyl)aniline), was ～66-times as active as diphenyl sulfone (Ki = 24.3 nM). Addition of a piperazinyl moiety in the para-position relative to the sulfonyl group in compound 10m (N-methyl-2-(phenylsulfonyl)-5-piperazin-1-ylaniline) led to a further 150-fold increase in potency (Ki = 0.16 nM) to block the serotonin-induced response of HEK-293 cells that were stably transfected with the human recombinant 5-HT6 receptor.
- Ivachtchenko, Alexandre,Golovina, Elena,Kadieva, Madina,Mitkin, Oleg,Tkachenko, Sergei,Okun, Ilya
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p. 4614 - 4627
(2013/07/26)
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- Silica-supported molybdenum complex: A novel, selective and reusable organic-inorganic hybrid catalyst for eco-friendly oxidation of sulfides and olefins
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A novel, highly efficient and reusable molybdenum based catalyst has been synthesized by covalent grafting of 2,6-diacetylpyridine-monosalicyloylhydrazone onto functionalized silica followed by complexation with MoO 2(acac)2, and the resulting organic-inorganic hybrid material was found to be highly effective catalyst for oxidation of various sulfides and olefins to their corresponding sulfoxides/sulfones and epoxides, respectively. The catalyst was characterized by elemental analysis (CHN), diffuse reflectance UV-Vis, 13C CPMAS NMR spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM) and BET surface area analysis, energy dispersive X-ray fluorescence (ED-XRF), Fourier-transform infrared (FT-IR) and atomic absorption spectroscopy (AAS). Mild reaction conditions, high turnover frequency, high selectivity, easy recovery and reusability of the catalyst render the present protocol very useful to address the industrial needs and environmental concerns.
- Sharma,Pandey, Amit,Gulati, Shikha
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- Exploration of the structure-activity relationship of the diaryl anilide class of ligands for translocator protein - Potential novel positron emitting tomography imaging agents
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A series of novel ligands based on the diaryl anilide (DAA) class of translocator protein (TSPO) ligands was synthesised and evaluated as potential positron emitting tomography (PET) ligands for imaging TPSO in vivo. Fluorine-18 labelling of the molecules was achieved using direct radiolabelling or synthon based labelling approaches. Several of the ligands prepared have promising profiles as potential TSPO PET imaging ligands and will be evaluated further as potential clinical imaging agents.
- Wadsworth, Harry,Jones, Paul A.,Chau, Wai-Fung,Durrant, Clare,Morisson-Iveson, Veronique,Passmore, Joanna,O'Shea, Dennis,Wynn, Duncan,Khan, Imtiaz,Black, Andrew,Avory, Michelle,Trigg, William
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p. 5795 - 5800,6
(2020/07/30)
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- A mild and efficient synthesis of aryl sulfones from aryl chlorides and sulfinic acid salts using microwave heating
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The CuCl-catalyzed coupling of aryl chlorides and sulfinic acid salts provides a simple and extremely efficient route to unsymmetrical aryl sulfones in high to excellent yields under microwave irradiation within 3-30 minutes. Georg Thieme Verlag Stuttgart · New York.
- Yuan, Yan-Qin,Guo, Sheng-Rong
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supporting information; experimental part
p. 2750 - 2756
(2011/12/04)
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- Simple and Friendly Sulfones Synthesis Using Aqueous Hydrogen Peroxide with a Reusable Keggin Molybdenum Heteropolyacid, Immobilized on Aminopropyl-Functionalized Silica
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Keggin molybdenum heteropolyacid (H3PMo12O 40), immobilized on aminopropyl-functionalized silica catalysts, were made using two immobilization methods: incipient wetness and equilibrium adsorption. The material prepared for the equilibrium adsorption technique was found to be a highly efficient, ecofriendly, and recyclable heterogeneous catalyst for the selective oxidation of sulfides to sulfones in excellent yields, under mild reaction condition using 35% w/v aqueous hydrogen peroxide as the oxidant.
- Palermo, Valeria,Romanelli, Gustavo P.,Vazquez, Patricia G.
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scheme or table
p. 3258 - 3268
(2010/04/26)
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- Anion-functionalized ionic liquids enhance the cui-catalyzed cross-coupling reaction of sulfinic acid salts with aryl halides and vinyl bromides
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An easily accessible, anion-functionalized ionic liquid, 1-ethyl-3-methylimidazolium (S)-2-amino-3-methylbutyric acid salt, [emim][Val], has been demonstrated to be an efficient additive for the CuI-catalyzed coupling reaction of sulfinic acid salts with aryl iodides, aryl bromides and vinyl bromides, leading to the formation of sulfones in good yields. Georg Thieme Verlag Stuttgart.
- Bian, Ming,Xu, Fada,Ma, Cheng
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p. 2951 - 2956
(2008/03/13)
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- 2-Amino-6-arylsulfonylbenzonitriles as non-nucleoside reverse transcriptase inhibitors of HIV-1
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A series of 2-amino-5-arylthiobenzonitriles (1) was found to be active against HIV-1. Structural modifications led to the sulfoxides (2) and sulfones (3). The sulfoxides generally showed antiviral activity against HIV-1 similar to that of 1. The sulfones, however, were the most potent series of analogues, a number having activity against HIV-1 in the nanomolar range. Structural-activity relationship (SAR) studies suggested that a meta substituent, particularly a meta methyl substituent, invariably increased antiviral activities. However, optimal antiviral activities were manifested by compounds where both meta groups in the arylsulfonyl moiety were substituted and one of the substituents was a methyl group. Such a disubstitution led to compounds 3v, 3w, 3x, and 3y having IC50 values against HIV-1 in the low nanomolar range. When gauged for their broad-spectrum antiviral activity against key non-nucleoside reverse transcriptase inhibitor (NNRTI) related mutants, all the di-meta-substituted sulfones 3u-z and the 2-naphthyl analogue 3ee generally showed single-digit nanomolar activity against the V106A and P236L strains and submicromolar to low nanomolar activity against strains E138K, V108I, and Y188C. However, they showed a lack of activity against the K103N and Y181C mutant viruses. The elucidation of the X-ray crystal structure of the complex of 3v (739W94) in HIV-1 reverse transcriptase showed an overlap in the binding domain when compared with the complex of nevirapine in HIV-1 reverse transcriptase. The X-ray structure allowed for the rationalization of SAR data and potencies of the compounds against the mutants.
- Chan,Hong,Hunter III,Orr,Cowan,Sherman,Sparks,Reitter,Andrews III,Hazen,St. Clair,Boone,Ferris,Creech,Roberts,Short,Weaver,Ott,Ren,Hopkins,Stuart,Stammers
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p. 1866 - 1882
(2007/10/03)
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- A mild and efficient procedure for the oxidation of organic sulfides to sulfones by use of urea-hydrogen peroxide/trifluoroacetic anhydride system
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Selective, mild and safe oxidation of dialkyl-, diaryl- and alkyl-aryl sulfides to the corresponding sulfones was achieved by using of urea- H2O2/trifluoroacetic anhydride system.
- Balicki, Roman
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p. 2235 - 2239
(2007/10/03)
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- An efficient method for the oxidation of organic sulfides to sulfones
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Mild and safe oxidation of dialkyl-, diaryl- and alkyl-aryl sulfides (1a-m) to the corresponding sulfones (2a-m)by using urea-hydrogen peroxide/formic acid system is reported. Wiley-VCH Verlag GmbH, 1999.
- Balicki, Roman
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p. 184 - 185
(2007/10/03)
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- 1H and 13C NMR Study of Substituted Effects in 2- and 3-Substituted Diphenyl Sulphides and Sulphones and 4-Substituted 2',6'-Dimethyldiphenyl Sulphides
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The proton and carbon NMR spectra of nine 2-substituted diphenyl sulphides (S-2-X), seven 3-substituted diphenyl sulphides (S-3-X), nine 2-substituted diphenyl sulphones (SO2-2-X), nine 3-substituted diphenyl sulphones (SO2-3-X) and nine 4-substituted-2',6'-dimethyldiphenyl sulphides (Me2-S-4-X) were obtained.Correlations of the 1H and 13C chemical shifts were made with benzene substituent-induced chemical shifts (Lynch plots) and Hammett and dual-substituent parameters and the results were compared with those of 4-substituted diphenyl sulphides (S-4-X) and sulphones (SO2-4-X).The main conclusions are as follows: (i) the transmission of the substituent effects in substituted diphenyl sulphides decreases in the order S-4-X ca.S-2-X > Me2-S-4-X > S-3-X; (ii) the inductive effects are transmitted to a larger extent than the resonance effects to the unsubstituted ring in 3-substituted diphenyl sulphides, while the reverse trend is observed in other substituted diphenyl sulphides; (iii) in 2-methoxy-, 2-chloro-, 2-bromo- and 2-nitrodiphenyl sulphides, an increase in the size of the substituent causes an upfield shift for H-6 ascribable to the repulsion between the lone pairs of electrons on the sulphur and the substituent and its influence on the conformation; (iv) the diminished transmission of substituent effects to the remote rings in 4-substituted 2',6'-dimethyldiphenyl sulphides is probably due to the orthogonal orientation of the rings; and (v) the signal due to the H-6 of 2-substituted diphenyl sulphones suffers a downfield shift with an increase in the size of the substituent, this being ascribable to the increasing steric interaction between the 2-substituent and the sulphonyl oxygen and consequent changes in the conformation. - Keywords: NMR; 1H NMR; 13C NMR; diphenyl sulphides; diphenyl sulphones; ?-polarization
- Perumal, Subbu,Chandrasekaran, Ramasubbu,Vijayabaskar, Veerappan,Wilson, David A.
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p. 779 - 790
(2007/10/03)
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- Sulphinyl, Sulphonyl, and Sulphonium Groups as Leaving Groups in Aromatic Nucleophilic Substitutions
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The kinetics of hydrolysis of mononitrophenyl sulphoxides, sulphones, and sulphonium methylsulphate by sodium hydroxide have been measured in 25percent aqueous dioxan.The mobility order of the leaving groups (+SMe2 >/= SO ca. SO2 for p-nitro-derivatives, and SO > SO2 for o-nitro-derivatives) are discussed in terms of electronic and steric effects.
- Chisari, Alfio,Maccarone, Emanuele,Parisi, Giovanni,Perrini, Giancarlo
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p. 957 - 960
(2007/10/02)
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- 149. Notizen zur Synthese von 2-Aminophenylsulfonen
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Syntheses of the alkyl, cycloalkyl and aryl 2-aminophenyl sulfones 10 were achieved by oxidation of the corresponding 2-nitrophenyl sulfides 7 to the 2-nitrophenyl sulfones 9 followed by ethanolic Bechamp-reduction.The sulfides 7 in turn were obtained by either reactions of 2-nitro-thiophenol (8) with the appropriate alkyl and cycloalkyl halides or of 2-chloro-nitrobenzene (5) with the relevant thiols.Condensation of 2-nitrobenzenesulfinic acid (3) with bromoacetic acid in aqueous alkaline solution led - presumably via 2-nitrophenylsulfonylacetic acid (4) - to methyl2-nitrophenyl sulfone (1), reduction of which gave 2-aminophenyl methyl sulfone (2).Treatment of 2-aminothiophenol (11) with t-butyl alcohol in aqueous sulfuric acid gave 2-aminophenyl t-butyl sulfide (12), which was acetylated to o-t-butylthio-acetanilide (13).Oxidation of the latter to o-t-butylsulfonyl-acetanilide (14) followed by hydrolysis led to 2-aminophenyl t-butyl sulfone (15).
- Courtin, Alfred,Tobel, Hans-Rudolf von,Auerbach, Guenther
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p. 1412 - 1419
(2007/10/02)
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