- Metal-free sulfonylation of arenes with: N -fluorobenzenesulfonimide via cleavage of S-N bonds: expeditious synthesis of diarylsulfones
-
A novel metal-free sulfonylation of arenes with N-fluorobenzenesulfonimide (NFSI) toward the synthesis of diarylsulfones has been developed. The reaction represents a rare example of sulfonylation reaction using NFSI as an efficient sulfonyl donor and the first example of acid-mediated sulfonylation of unactivated arenes with NFSI via selective cleavage of S-N bonds. This protocol provides a concise approach for the construction of pharmaceutically and biologically important diarylsulfones. Applications in the functionalization of natural products (e.g., β-estradiol) and in the synthesis of a key intermediate to an inhibitor of farnesyl-protein transferase, as well as in the gram-scale synthesis of the EPAC2 antagonist, are demonstrated. This journal is
- Feng, Yueji,Tuo, Yanyan,Zhang, Xiaohui,Zheng, Qing-Zhong
-
supporting information
p. 768 - 772
(2022/02/03)
-
- Sulfonylation of Bismuth Reagents with Sulfinates or SO2through BiIII/BiV Intermediates
-
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
-
supporting information
p. 2400 - 2404
(2021/07/28)
-
- Heterogeneous copper-catalyzed synthesis of diaryl sulfones
-
A carbon-supported copper nanoparticle (Cu-NP) with high catalytic activity for the synthesis of diaryl sulfones is reported. For the first time, this Cu-NP is proved to be able to effectively promote the reaction of arylboronic acids and arylsulfonyl hydrazides to generate diaryl sulfones at room temperature. The reaction shows excellent substrate universality, and substrates with different substituents can undergo the reaction smoothly, leading to the desired products in good yields. The Cu-NP is found to be made of low valence Cu based on XRD. Hence, the reaction catalyzed by the Cu-NP is believed to involve a Cu-mediated organometallic cycle.
- Gong, Xinchi,Qu, Lingling,Shen, Zhengqi,Wang, Ganghu,Zhu, Chunyin
-
supporting information
p. 10662 - 10668
(2021/12/27)
-
- Catalyst-free arylation of sulfonamidesviavisible light-mediated deamination
-
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
-
p. 9556 - 9560
(2021/07/25)
-
- Nano copper catalyzed synthesis of symmetrical/unsymmetrical sulfones from aryl/alkyl halides and p-toluenesulfonylmethylisocyanide: TosMIC as a tosyl source
-
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
-
-
- Facile synthesis of diarylsulfones from arenes and 3CdSO4·xH2O via mechanochemistry
-
A variety of substituted diarylsulfones could be synthesized by simple arenes and 3CdSO4·xH2O in the presence of P2O5 under high-speed ball milling. It was suggest the aromatic sulfonation was performed by arene and in situ generated H2SO4, following-up by electrophilic substitution with another arene to give diarylsulfone.
- Qin, Shuai,Zhang, Pu,Qin, Yu-Jun,Guo, Zhi-Xin
-
supporting information
(2020/01/06)
-
- Regiospecific Cleavage of S-N Bonds in Sulfonyl Azides: Sulfonyl Donors
-
Sulfonyl azides have been widely used as sulfonamido, diazo, and azido donors, as well as all-nitrogen 1,3-dipoles donors in synthetic chemistry. Here, the sulfonyl azides were used as efficient sulfonyl donors, which is very unusual. Trifluoromethanesulfonic acid-induced formation of the sulfonyl cation reactive species from sulfonyl azides was developed and used for the first time to couple various inactivated arenes to prepare sulfones at ambient temperature.
- Zhang, Zhiguo,Wang, Songnan,Zhang, Yong,Zhang, Guisheng
-
p. 3919 - 3926
(2019/03/29)
-
- Copper-mediated sulfonylation of aryl iodides and bromides with arylsulfonyl hydrazides in PEG-400
-
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
-
p. 10953 - 10957
(2018/07/06)
-
- Synthesis of diaryl sulfones at room temperature: Cu-catalyzed cross-coupling of arylsulfonyl chlorides with arylboronic acids
-
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
-
p. 1539 - 1542
(2015/05/27)
-
- A highly active and easily recoverable chitosan@copper catalyst for the C-S coupling and its application in the synthesis of zolimidine
-
Aryl sulfones were synthesized using a highly active and easily recoverable heterogeneous Cu catalyst which was prepared by simply stirring an aqueous suspension of chitosan in water with copper salts. The chitosan@copper catalyst catalyzed the coupling reactions of aryl halides with sodium sulfinates to readily give the corresponding sulfones in good to excellent yields. The highly active catalyst can be reused many times without losing its catalytic activity. In addition, by using this protocol, the marketed drug zolimidine (antiulcer) could be synthesized easily. This journal is the Partner Organisations 2014.
- Shen, Chao,Xu, Jun,Yu, Wenbo,Zhang, Pengfei
-
supporting information
p. 3007 - 3012
(2014/06/10)
-
- Sulfonylation of aromatic compounds with methyl p-toluenesulfonate as a sulfonylating precursor
-
We have developed Friedel-Crafts (FC) sulfonylation of aromatic compounds with methyl p-toluenesulfonate as a sulfonylating precursor. In this procedure, methyl p-toluenesulfonate was treated and activated with pyridine to produce N-methylpyridinium p-toluenesulfonate as a sulfonylation reagent. Reactivity of this salt for the sulfonylation of mesitylene was investigated in the presence of three different promoters, such as triflic anhydride, dimethylsulfide ditriflate, and triphenylphosphine ditriflate (TPPD). All of the promoters show chemoselectivity and among them, TPPD presents a chemoselectivity in FC sulfonylation. Iranian Chemical Society 2012.
- Khodaei,Nazari
-
p. 507 - 512
(2013/02/22)
-
- Sulfonylation of aromatic compounds with sulfonic acids using silica gel-supported AlCl3 as a heterogeneous Lewis acid catalyst
-
Silica gel-supported aluminum chloride (SiO2-AlCl3) has been shown to be a mild, efficient, and chemoselective heterogeneous Lewis acid catalyst for direct conversion of arenes to sulfones using sulfonic acids as sulfonylating agents. The catalyst can be prepared easily with cheap starting materials and is stable (as a bench-top catalyst) and reusable.
- Parvanak Boroujeni, Kaveh
-
experimental part
p. 197 - 203
(2010/11/05)
-
- Polystyrene supported Al(OTf)3: A stable, efficient, selective, and reusable catalyst for sulfonylation of arenes with sulfonic acids
-
Cross-linked polystyrene supported aluminium triflate (Ps-Al(OTf) 3) was found to be an efficient and chemoselective heterogeneous Lewis acid catalyst for the direct conversion of arenes to sulfones using sulfonic acids as sulfonylating agents. The solid acid catalyst is stable (as a bench top catalyst) and can be easily recovered and reused without appreciable change in its efficiency.
- Boroujeni, Kaveh Parvanak
-
experimental part
p. 1887 - 1890
(2010/11/18)
-
- MoO2Cl2 as a novel catalyst for Friedel-Crafts acylation and sulfonylation
-
The use of MoO2Cl2 as a novel catalyst for Friedel-Crafts acylation and sulfonylation is described. A series of aromatic ketones and sulfones were prepared in moderate to good yields using acyl chloride or sulfonyl chloride in the presence of MoO2Cl2 (20 mol %), under solvent-free conditions.
- de Noronha, Rita G.,Fernandes, Ana C.,Rom?o, Carlos C.
-
experimental part
p. 1407 - 1410
(2009/06/18)
-
- Sulfonylation of arenes with sulfonamides
-
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
-
p. 5385 - 5388
(2008/12/21)
-
- Highly selective catalytic Friedel-Crafts sulfonylation of aromatic compounds using a FeCl3-based ionic liquid
-
Friedel-Crafts sulfonylation of aromatic compounds was carried out using FeCl3-based ionic liquid. These liquids serve as efficient media as well as Lewis acid catalyst.
- Bahrami, Kiumars,Khodei, Mohammad Mehdi,Shahbazi, Fomeida
-
p. 3931 - 3934
(2008/09/21)
-
- Copper-Catalyzed Sulfonylation of Arylboronic Acids in Ionic Liquids
-
Cupric acetate in ionic liquids (ILs) catalyzes coupling reaction of arylboronic acids with sulfinic acid salts to afford aryl sulfones in good yields under ambient conditions. This mild and efficient cross-coupling reaction gives access to a wide range of alkylaryl and diaryl sulfones in good yields. The use of ionic liquid allows for easy separation of the product and recycling of copper catalyst.
- Kantam, M. Lakshmi,Neelima,Sreedhar,Chakravarti, Rajashree
-
experimental part
p. 1455 - 1458
(2009/04/07)
-
- Cross-coupling of organoboronic acids and sulfinate salts using catalytic copper(II) acetate and 1,10-phenanthroline: synthesis of aryl and alkenylsulfones
-
A mild method for the preparation of aryl and alkenylsulfones from the cross-coupling reaction of organoboronic acids and sodium sulfinate salts is described. Optimized conditions utilize a catalytic amount of copper(II) acetate monohydrate with 1,10-phenanthroline as ligand in the presence of 4 ? molecular sieves. A co-solvent mixture of dichloromethane/DMSO was used, with reactions occurring at 40 °C under an atmosphere of oxygen. Reaction at room temperature also yields sulfone product, but in lower yields. The method tolerates a variety of substituents on the organoboronic acid, including amide, aldehyde, halide and nitro functionalities, as well as ortho-substituents. In general, the reaction is found to be less efficient using arylboronic acids bearing electron-withdrawing substituents, or using aryltrifluoroborate salts.
- Huang, Fang,Batey, Robert A.
-
p. 7667 - 7672
(2008/02/08)
-
- Palladium-catalyzed desulfinylative Negishi C-C bond forming cross-couplings of sulfonyl and organozinc chlorides
-
Arene-, phenylmethane- and alkenesulfonyl chlorides are suitable electrophilic reagents in desulfinylative carbon-carbon bond formation cross-coupling reactions with organozinc reagents.
- Dubbaka, Srinivas Reddy,Vogel, Pierre
-
p. 3345 - 3348
(2007/10/03)
-
- Direct sulfonylation of aromatic rings with aryl or alkyl sulfonic acid using supported P2O5/Al2O3
-
Direct sulfonylation of aromatic rings with aryl or alkyl sulfonic acid supported P2O5/Al2O3 (w/w 50%) under heterogeneous conditions in short reaction time and high yields. Copyright Taylor & Francis Inc.
- Hajipour, Abdol R.,Zarei, Amin,Khazdooz, Leila,Pourmousavi, Seied A.,Mirjalili, Bi Bi F.,Ruoho
-
p. 2029 - 2034
(2007/10/03)
-
- Unsymmetrical diaryl sulfones through palladium-catalyzed coupling of aryl boronic acids and arylsulfonyl chlorides
-
A simple and efficient method for the synthesis of unsymmetrical diaryl sulfones using the palladium-catalyzed coupling of aryl boronic acids and arylsulfonyl chlorides has been developed. High product yields, a short reaction time, and mild reaction conditions are important features of this method.
- Bandgar,Bettigeri, Sampada V.,Phopase, Jaywant
-
p. 2105 - 2108
(2007/10/03)
-
- Fe-pillared bentonite-an efficient catalyst for sulfonylation of arenes using aryl and alkyl sulfonyl chlorides
-
Fe-pillared bentonite (Fe-PILC) was shown to be an extremely efficient catalyst for the sulfonylation of activated as well as unactivated carbocyclic aromatic compounds and heterocyclic aromatic compounds. The catalyst was also found to be recyclable.
- Singh, Devendrapratap U.,Singh, Pankajkumar R.,Samant, Shriniwas D.
-
p. 9079 - 9082
(2007/10/03)
-
- Method for acylation or sulphonylation of an aromatic compound
-
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.
- -
-
Page column 25
(2008/06/13)
-
- Acylation and related reactions under microwaves. 4. Sulfonylation reactions of aromatics
-
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
-
p. 421 - 425
(2007/10/03)
-
- Indium-catalysed aryl and alkyl sulfonylation of aromatics
-
Commercially available indium (III) triflate is shown to be an extremely efficient catalyst for the sulfonylation of both activated and deactivated aromatics.
- Frost,Hartley,Whittle
-
p. 830 - 832
(2007/10/03)
-
- Zinc-mediated fast sulfonylation of aromatics
-
Zn dust-mediated Friedel-Crafts sulfonylation of aromatic compounds with p-toluenesulfonyl chloride was carried out to give corresponding sulfones in good yields. Isolation of pure products by simple filtration and evaporation is an important feature of this method.
- Bandgar,Kasture
-
p. 1065 - 1068
(2007/10/03)
-
- Friedel - Crafts sulfonylation in 1-Butyl-3-methylimidazolium chloroaluminate ionic liquids
-
1-Butyl-3-methylimidazolium chloroaluminate ionic liquids have been employed as an unconventional reaction media and as Lewis acid catalyst for Friedel-Crafts sulfonylation reaction of benzene and substituted benzenes with 4-methyl benzenesulfonyl chloride. The substrates exhibited enhanced reactivity, furnishing almost quantitative yields of diaryl sulfones, under ambient conditions. Studies concerning the effect of Lewis acidity of the ionic liquid on the initial extent of conversion of this reaction has been carried out. 27Al NMR spectroscopy has been exploited as a tool to investigate the mechanistic details of the reaction. 27Al NMR spectral studies show the predominance of [Al2Cl7]- species in [bmim] Cl-AlCl3, N = 0.67, acidic ionic liquid in the presence of 4-methyl benzenesulfonyl chloride, and after the reaction with the aromatic hydrocarbon, [AlCl4]- species predominates. This change in speciation of aluminum can be attributed to the interaction of the Lewis acidic species [Al2Cl7]- of the ionic liquid with the formed HCl during the sulfonylation reaction, which is evidenced by the control experiment. Preliminary investigations on Friedel-Crafts acylation further substantiate the argument.
- Nara,Harjani,Salunkhe
-
p. 8616 - 8620
(2007/10/03)
-
- An efficient method for aromatic Friedel-Crafts alkylation, acylation, benzoylation, and sulfonylation reactions
-
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
-
p. 241 - 247
(2007/10/03)
-
- Friedel-Crafts sulfonylation of aromatics catalysed by solid acids: An eco-friendly route for sulfone synthesis
-
A mild and efficient catalytic method for Friedel-Crafts sulfonylation of arenes to the corresponding sulfones using a catalytic amount of reusable solid acid and arene- or alkanesulfonyl chlorides, sulfonic anhydrides and sulfonic acids as sulfonylating agents is described. Solid acids enable formation of a sulfone by the reaction of a sulfonic acid and an arene for the first time. In pursuit of the development of the best catalytic system, various metal-exchanged K10 montmorillonites and synthetic zeolites such as zeolite beta, zeolite Y and ZSM-5 have been screened for Friedel-Crafts sulfone synthesis. Fe3+-montmorillonite in the family of clays and zeolite beta in the family of zeolites exhibit higher activity. The activity is correlated to the presence of the right mix of Bronsted and Lewis acidic sites. The regioselective sulfonylation of toluene and naphthalene are studied in which para and beta selectivities are observed respectively. The Royal Society of Chemistry 2000.
- Choudary, Boyapati M.,Chowdari, N. Sreenivasa,Kantam, M. Lakshmi
-
p. 2689 - 2693
(2007/10/03)
-
- Bismuth(III) halides: Remarkable doping agents for triflic acid in the catalytic sulfonylation of arenes
-
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
-
p. 9233 - 9234
(2007/10/03)
-
- Friedel-crafts alkylation and acylation in the absence of solvent
-
A short and efficient synthetic route, for alkylation and acylation of aromatic compounds in the absence of solvent is developed. According to the reaction system and conditions used, different alkyl-, and acyl arenes are obtained in moderate to good yields. The structures are assigned by 1H and 13C NMR spectroscopy.
- Ghiaci,Asghari
-
p. 2213 - 2220
(2007/10/03)
-
- 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
-
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.
-
p. 367 - 372
(2007/10/03)
-
- Synthesis and Reactions of Arylcarbonic Fluorosulfonic Anhydrides
-
In dichloromethane at 0 deg C, the acyl fluorides 3 insert sulfur trioxide to form the thermolabile acylcarbonic fluorosulfonic anhydrides 4 in good yield.Acylation of non-activated arenes with the anhydrides 4 is impossible since they decompose upon warming into constituent compounds; with the SO3 thus liberated, diarylsulfones 6 are formed.
- Effenberger, Franz,Huthmacher, Klaus,Keil, Michael
-
p. 1967 - 1971
(2007/10/02)
-
- Novel Sulfonylation reagent: Sulfuric Acid-Hexafluoroacetic Anhydride
-
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
-
p. 114 - 115
(2007/10/02)
-