- Sulfonylation of Bismuth Reagents with Sulfinates or SO2through BiIII/BiV Intermediates
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Studies to explore the catalytic activities of main-group elements are attractive. We report here our study of sulfonylation of bismuth reagents with sulfinates or SO2 surrogates. Under oxidative conditions, triarylbismuthines and sulfinates were transformed into diaryl sulfones. A transition-metal-like two-electron redox process at the Bi center was achieved in this reaction. Sulfur dioxide generated in situ can also replace sulfinates to deliver the corresponding symmetric diaryl sulfones. A rational mechanism for this reaction was also proposed that involves a Bi(III)-Bi(V) manifold.
- Zhao, Fengqian,Wu, Xiao-Feng
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supporting information
p. 2400 - 2404
(2021/07/28)
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- Catalyst-free arylation of sulfonamidesviavisible light-mediated deamination
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A novel arylation of sulfonamides with boronic acids to afford numerous diaryl sulfonesviaa visible light-mediated N-S bond cleavage other than the typical transition-metal-catalyzed C(O)-N bond activation is described. This methodology, which represents the first catalyst-free protocol for the sulfonylation of boronic acids, is characterized by its simple reaction conditions, good functional group tolerance and high efficiency. Several successful examples for the late-stage functionalization of diverse sulfonamides indicate the high potential utility of this method in pharmaceutical science and organic synthesis.
- Ding, Hao,Ding, Qiuping,Du, Xian,Li, Yi-Hui,Liu, Bing-Zhe,Lu, Shi-Man,Luo, Yong,Qi, Wan-Ying,Xu, Xiao-Hong,Xue, Can,Yuan, Han,Zhen, Jing-Song
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p. 9556 - 9560
(2021/07/25)
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- Nano copper catalyzed synthesis of symmetrical/unsymmetrical sulfones from aryl/alkyl halides and p-toluenesulfonylmethylisocyanide: TosMIC as a tosyl source
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A magnetically induced nano copper-catalyzed efficient and mild route for the synthesis of diaryl and alkyl/aryl sulfones from aryl/alkyl halides and tosylmethyl isocyanide (TosMIC) has been developed. A variety of aryl and alkyl sulfones have been obtained in very good to excellent yields. Sulfones containing molecules have medicinal relevance as they are known to possess various activities such as antifungal, anti-HIV, antitumor, and anticancer. Herein, a magnetically induced nano copper-catalyzed efficient and mild route for the synthesis of biaryl and alkyl/aryl sulfones from aryl/alkyl halides and tosylmethyl isocyanide (TosMIC) has been developed. A variety of aryl and alkyl sulfones have been obtained in very good to excellent yields. In this newly developed protocol TosMIC acts as sulfonyl source. The catalyst can magnetically be recovered and recycled five times without significant loss in activity.
- Phanindrudu, Mandalaparthi,Jaya, Pogula,Likhar, Pravin R.,Tiwari, Dharmendra Kumar
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- Method for preparing diphenyl sulfone compound through catalysis of palladium acetate
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The invention discloses a method for preparing a diphenyl sulfone compound shown in formula (III) through catalysis of palladium acetate. The method comprises the following steps: fully reacting a bromobenzene compound as shown in formula (I), sodium sulfate and a benzoic acid compound as shown in formula (II) in a reaction medium with dimethylformamide (DMF) as a solvent under the action of palladium acetate as a catalyst and alkali metal carbonate as a base to prepare a reactant, and carrying out aftertreatment on the reactant to prepare the diphenyl sulfone compound. The catalyst is 20-mol%equivalent of the palladium acetate, and the alkali metal carbonate is cesium carbonate; in a reaction formula as shown in specification, R1 is selected from one of the following components: hydrogenand methyl; R2 is selected from one of the following components: hydrogen, methyl, methoxyl and trifluoromethoxy; the raw materials are simple, convenient and easy to obtain, and the preparation conditions are mild; the cost is low, and the requirement on equipment is low; aftertreatment is facilitated; and a catalytic system has wide adaptability and is suitable for large-scale industrial production.
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Paragraph 0019; 0020
(2019/07/04)
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- A practical synthesis of aryl sulfones via cross-coupling of sulfonyl hydrazides with aryltriazenes using copper/ionic liquid combination
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A new and efficient approach adopting copper-catalyzed cross-coupling of sulfonyl hydrazides with aryltriazenes has been developed to synthesize aryl sulfones using Br?nsted acidic ionic liquid as promoter under ambient conditions. The process employs stable and easy to handle reacting partners, and is endowed with broad substrate scope.
- Pandey, Anand Kumar,Kumar, Saurabh,Singh, Rahul,Singh, Krishna Nand
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supporting information
p. 6704 - 6709
(2018/10/15)
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- Copper-mediated sulfonylation of aryl iodides and bromides with arylsulfonyl hydrazides in PEG-400
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Sulfonylation using stable and readily available arylsulfonyl hydrazides and aryl iodides or bromides mediated by cupric acetate has been achieved. Using polyethylene glycol (PEG-400) as an eco-friendly medium, the coupling reaction could afford a series of unsymmetrical diaryl sulfones in moderate to good yields without the presence of additional ligands and base.
- Wu, Xiangmei,Wang, Yan
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p. 10953 - 10957
(2018/07/06)
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- Synthesis of diaryl sulfones at room temperature: Cu-catalyzed cross-coupling of arylsulfonyl chlorides with arylboronic acids
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An efficient and convenient method for the synthesis of diaryl sulfones was developed through the Cu-catalyzed cross-couplings of arylsulfonyl chlorides and arylboronic acids at room temperature in open air. This method is characterized by the use of inexpensive and readily available catalyst and substrates, mild reaction conditions, wide functionality tolerance, short reaction times for most substrates, and moderate to good yields. Stitch it up with copper: An efficient and convenient method for the synthesis of diaryl sulfones was developed through the Cu-catalyzed cross- couplings of arylsulfonyl chlorides and arylboronic acids at room temperature in open air.
- Hu, Feng,Lei, Xiangyang
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p. 1539 - 1542
(2015/05/27)
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- Palladium-catalyzed three-component diaryl sulfone synthesis exploiting the sulfur dioxide surrogate DABSO
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SO(2) efficient: A three-component palladium-catalyzed coupling of aryl lithium compounds; sulfur dioxide (provided by the easy-to-handle solid surrogate, DABSO); and aryl, heteroaryl, and alkenyl (pseudo)halides yields a diverse library of sulfones. An electron-poor XantPhos-type ligand suppresses aryl-aryl exchange and is key to obtaining high yields.
- Emmett, Edward J.,Hayter, Barry R.,Willis, Michael C.
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supporting information
p. 12679 - 12683
(2013/12/04)
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- Sulfonylation of arenes with sulfonamides
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In the presence of triflic anhydride, sulfonylation of arenes with sulfonamides proceeded smoothly in Cl2CHCHCl2 at 80-140 °C, which gave rise to the desired products in good to excellent yields.
- Yao, Bangben,Zhang, Yuhong
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p. 5385 - 5388
(2008/12/21)
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- Unsymmetrical diaryl sulfones and aryl vinyl sulfones through palladium-catalyzed coupling of aryl and vinyl halides or triflates with sulfinic acid salts
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The palladium-catalyzed reaction of sulfinic acid salts with a wide variety of aryl and vinyl halides or triflates provides unsymmetrical diaryl sulfones and aryl vinyl sulfones in good to excellent yields. The reaction is strongly influenced by the presence of nBu4NCl, and the use of Xantphos, a rigid bidentate ligand with a wide natural bite angle, was found to be crucial for the success of the reaction. With neutral, electron-rich, and electron-poor aryl iodides best results were obtained by using Pd 2(dba)3, Xantphos, Cs2CO3, and nBu4NCl, in toluene at 80 °C. Two general procedures were employed with aryl bromides and triflates: sodium p-toluenesulfinate, Pd2(dba)3, Xantphos, Cs2CO3, 120 °C, in toluene with nBu4NCl (procedure A: neutral, electron-rich, and slightly electron-poor aryl bromides or triflates) and without nBu4NCl (procedure B: electron-poor aryl bromides or triflates). With vinyl triflates best results were obtained at 60 °C omitting nBu4NCl.
- Cacchi, Sandro,Fabrizi, Giancarlo,Goggiamani, Antonella,Parisi, Luca M.,Bernini, Roberta
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p. 5608 - 5614
(2007/10/03)
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- An efficient palladium-catalyzed synthesis of unsymmetrical diaryl sulfones from aryl bromides/triflates and arenesulfinates
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The palladium-catalyzed coupling of arenesulfinate salts and aryl bromides or triflates provides a simple and extremely efficient route to unsymmetrical diaryl sulfones. The reaction was found to be strongly influenced by the presence of n-Bu4NCl. The ammonium salt tends to favor the formation of sulfones with neutral, electron-rich and slightly electron-poor aryl bromides or triflates and to hamper the reaction with electron-poor aryl bromides or triflates.
- Cacchi, Sandro,Fabrizi, Giancarlo,Goggiamani, Antonella,Parisi, Luca M.
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p. 361 - 364
(2007/10/03)
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- Method for acylation or sulphonylation of an aromatic compound
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The present invention relates to a process for the acylation or sulphonylation of an aromatic compound. More particularly, the invention relates to a process for the acylation or sulphonylation of an activated or deactivated aromatic compound. The invention is applied to the preparation of aromatic ketones or sulphones. The process for the acylation or sulphonylation of an aromatic compound which consists in reacting at least one aromatic compound with an acylating or sulphonylating agent, in the presence of a Friedel-Crafts catalyst is characterized in that the acylation or sulphonylation reaction is carried out in liquid phase under microwave irradiation.
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Page column 25
(2008/06/13)
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- Unsymmetrical Diaryl Sulfones through Palladium-Catalyzed Coupling of Aryl Iodides and Arenesulfinates
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(Equation Presented) The palladium-catalyzed coupling of aryl iodides and arenesulfinates provides a simple and extremely efficient new route to unsymmetrical diaryl sulfones, usually isolated in high yield. The reaction tolerates a variety of functionalized aryl iodides, including those containing ether, ester, and nitro groups. The best results have been obtained by using Pd2(dba)3, Xantphos, Cs2CO3, and nBu4NCl in toluene at 80 °C.
- Cacchi, Sandro,Fabrizi, Giancarlo,Goggiamani, Antonella,Parisi, Luca M.
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p. 4719 - 4721
(2007/10/03)
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- Reactions of chlorine dioxide with organic compounds: Selective oxidation of sulfides to sulfoxides by chlorine dioxide
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A novel method for the selective oxidation of various types of sulfides to sulfoxides using chlorine dioxide as the oxidant is proposed.
- Kutchin,Rubtsova,Loginova
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p. 432 - 435
(2007/10/03)
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- A novel method for the construction of a benzene ring: A facile ring-closing reaction of (1E,3E,5E)-1-chloro-3-(p-tolylsulfonyl)-1,3,5-alkatrienes
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(1E,3E,5E)-1-Chloro-3-(p-tolylsulfonyl)-1,3,5-alkatrienes (1) underwent facile ring-closure followed by spontaneous removal of hydrogen chloride to form a benzene ring. This reaction sequence occurred at relatively low temperature.
- Ogura, Katsuyuki,Takeda, Mineko,Xie, Jian R.,Akazome, Motohiro,Matsumoto, Shoji
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p. 1923 - 1925
(2007/10/03)
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- An efficient method for aromatic Friedel-Crafts alkylation, acylation, benzoylation, and sulfonylation reactions
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Aromatic electrophilic substitution reactions such as alkylation, acylation, benzoylation, and sulfonylation were studied in the presence of a catalytic amount of Cu(OTf)2 and Sn(OTf)2. Cu(OTf)2 was very efficient for alkylation, acylation, and benzoylation reactions. However, in case of sulfonylation reactions, Sn(OTf)2 gave better results.
- Singh, Ravi P,Kamble, Rajesh M,Chandra, Kusum L,Saravanan,Singh, Vinod K
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p. 241 - 247
(2007/10/03)
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- Acylation and related reactions under microwaves. 4. Sulfonylation reactions of aromatics
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Solvent-free sulfonylation of benzene and its activated or deactivated derivatives were carried out under microwave (MW) irradiation and a catalytic amount of iron(III) chloride, which, under these conditions, is more, active than other metallic salts. With more reactive and/or nonvolatile reagents (anisole, xylenes, mesitylene) expeditious conditions (short reaction time at constant MW power without control of the temperature) were used. With less reactive and/or low-boiling reagents (benzene, toluene, halobenzenes), the rise in temperature and the increase of reaction time were controlled either by sequential MW irradiation or by a temperature order. It was shown that MWs cause preferential interactions with polar species present in the reaction, especially the aryl sulfone and its FeCl3-complexed form. A MW nonthermal effect was not observed when identical temperature gradients were produced by classical heating and MW irradiation, and if reaction temperature was strictly controlled.
- Marquie,Laporterie,Dubac,Roques,Desmurs
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p. 421 - 425
(2007/10/03)
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- Cycloaddition Reactions of 1-Phenylseleno-2-(p-toluenesulfonyl)ethyne
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1-Phenylseleno-2-(p-toluenesulfonyl)ethyne (1) is an effective dienophile and dipolarophile. It underwent facile Diels-Alder reactions with a variety of dienes to afford vicinal sulfone- and selenide-functionalized 1,4-cyclohexadienes. Unexpected regiochemistry that is the opposite of what is obtained with simple acetylenic sulfones was observed with several unsymmetrical dienes containing methyl or methoxy substituents at the 1- or 2-position. Acetylene 1 reacted with (trimethylsilyl)methyl azide, diazomethane, and 2,4,6-trimethylbenzonitrile N-oxide via 1,3-dipolar cycloadditions to afford the corresponding triazole, 1,2-diazole, and isoxazole products. It also underwent an ene reaction with β-pinene that showed anomalous regiochemistry compared to other acetylenic sulfones. The Diels-Alder cycloadducts obtained from the reaction of 1 with 2,3-dimethyl-1,3-butadiene and 1,3-cyclohexadiene were readily converted into the corresponding β-keto sulfones and ketones, thus rendering 1 as the synthetic equivalent of p-toluenesulfonylketene and ketene, respectively. Base-catalyzed elimination of TsOH from the Diels-Alder cycloadduct obtained with 2,3-dimethyl-1,3-butadiene afforded the corresponding aryl phenyl selenide, while the adduct from piperylene underwent oxidation to its selenoxide, followed by a Pummerer-type reaction to produce 2-(phenylseleno)-3-(p-toluenesulfonyl)toluene. The reaction of the bicyclic Diels-Alder product obtained from 1,3-cyclohexadiene with MeCu(SePh)Li resulted in substitution of the phenylseleno moiety by a methyl group, whereas similar treatment of the monocyclic adduct derived from piperylene effected elimination of PhSeH and aromatization.
- Back, Thomas G.,Bethell, Richard J.,Parvez, Masood,Taylor, Jerry A.,Wehrli, Daniel
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p. 7426 - 7432
(2007/10/03)
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- Bismuth(III) halides: Remarkable doping agents for triflic acid in the catalytic sulfonylation of arenes
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The catalytic activity of triflic acid has been dramatically increased by the addition of a catalytic amount of bismuth(III) chloride. Thus, the catalytic sulfonylation of arenes using the new system BiCl3-triflic acid has been successfully carried out while both components of this catalytic system are poorly active or inactive alone, which suggests a synergy between BiCl3 and triflic acid. Other bismuth halide-triflic acid systems proved to be active.
- Repichet,Le Roux,Dubac
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p. 9233 - 9234
(2007/10/03)
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- Electrophilic aromatic substitution. 14. [1] A kinetic, NMR, and raman study of the aluminum chloride-catalyzed reaction of p-toluene-sulfonyl chloride with benzene and toluene in dichloromethane
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Vacuum line kinetic studies of the reaction of p-toluenesulfonyl chloride and benzene or toluene, using aluminum chloride as the catalyst and dichloromethane as the solvent were determined at 25°C by means of gas chromatography The reaction is first-order in arene, tosyl chloride, and in AlCl3 as catalyst Noncompetitive results are kT/kB = 22 ± 7 with a product sulfone isomer distribution: ortho, 14 ± 1%, meta, 4.3 ± 0.2%, and para 82 ± 1%. With hexadeuteriobenzene kH/kO was determined to be 1.8 ± 0.1. Rate constant ratios and product isomer distributions were also determined competitively with AlCl3, kT/kB = 30 ± 2; % ortho, 13 ± 1.% meta, 4.0 ± 0.5; % para, 84 ± 3; with SbCl5, kT/kS = 40 ± 4;% ortho 10.3 ± 0.4; % meta, 4.7 ± 0.2; and % para, 85.0 ± 0.5. The kT/kB ratio for AlCl3 and the meta sulfone product per- centages for both AlCl3 and SbCl5 are considerably higher than those reported in the literature NMR and Raman studies suggest a molecular complex between p-tosyl chloride and AlCl3, with coordination through oxygen as the dominant species and the probable electrophile in CH2Cl2. A reaction mechanism consistent with the kinetic and spectroscopic results is pro- posed.
- DeHaan, Franklin P.,Ahn, Paul Y.,Kemnitz, Carl R.,Ma, Steven K.,Na, Jim,Patel, Bimal R.,Ruiz, Richard M.,Villahermosa, Randy M.
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p. 367 - 372
(2007/10/03)
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- Novel Sulfonylation reagent: Sulfuric Acid-Hexafluoroacetic Anhydride
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A mixture of sulfuric acid and hexafluoroacetic anhydride is an efficient reagent for the sulfonylation of aromatic compounds.
- Tyobeka, Themba E.,Hancock, Richard A.,Weigel, Helmut
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p. 114 - 115
(2007/10/02)
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