- Metal-free sulfonylation of arenes with: N -fluorobenzenesulfonimide via cleavage of S-N bonds: expeditious synthesis of diarylsulfones
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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
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supporting information
p. 768 - 772
(2022/02/03)
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- TosMIC and its derivatives as versatile sulfonylating agents for the synthesis of p-toluenesulfonylarenes from aryl halides and arylboronic acids
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An efficient copper(II) catalyzed sulfonyation of aryl halides has been achieved using TosMIC (p-toluenesulfonylmethyl isocyanide) as a sulfonylating agent. This newly developed sulfonylation approach provides an easy access for the synthesis of diaryl sulfones from aryl bromides, iodides and boronic acids with TosMIC under neutral conditions. This method is useful for the sulfonylation of aryl boronic acids under similar conditions. This is the first report on the sulfonylation of aryl bromides, iodides and boronic acids using TosMIC.
- Ravi Kumar,Ramesh,Banik, Swarnayu,Subba Reddy
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- Selective Synthesis of ortho-Substituted Diarylsulfones by Using NHC-Au Catalysts under Mild Conditions
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A single-step gold(I)-catalyzed chemoselective protocol to access ortho-substituted diarylsulfones has been established. Acenaphthoimidazolylidene gold complexes are effective catalysts for the arylsulfonylation of boronic acids by potassium metabisulfite (K2S2O5) and diaryliodonium salts to access (poly-)ortho-substituted diarylsulfones even in gram scale. Unlike the transition metal-catalyzed two-component coupling systems, the sterically hindered aryl groups in diaryliodonium salts are preferentially transferred over less bulky ones to form synthetically difficult targets, including those of pharmaceutical importance.
- Zhu, Haibo,Shen, Yajing,Wen, Daheng,Le, Zhang-Gao,Tu, Tao
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supporting information
p. 974 - 979
(2019/02/14)
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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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- MODULATORS OF EXCHANGE PROTEINS DIRECTLY ACTIVATED BY CAMP (EPACS)
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Embodiments of the invention are directed to compounds that inhibit an activity of EP AC proteins and methods of using the same. The inventors have developed a sensitive and robust high throughput screening (HTS) assay for the purpose of identifying EPAC specific inhibitors (Tsalkova et al. (2012) PLOS ONE 7(1 ):e30441).
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Paragraph 0173
(2013/08/28)
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- A Metal-Free and Microwave-Assisted Efficient Synthesis of Diaryl Sulfones
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An efficient and general protocol for the synthesis of diaryl sulfones via the metal-free coupling of readily available diaryliodonium salts and arenesulfinates in PEG-400 under microwave irradiation has been developed. Utilizing this metal-free and eco-friendly protocol, we have prepared various diaryl sulfones in high yields and shorter reaction times under mild conditions. Furthermore, the coupling of diaryliodonium with arenesulfinate salts with and without copper iodide provides a convenient access to various diaryl sulfones with high selectivity. Georg Thieme Verlag Stuttgart · New York.
- Kumar, Dalip,Arun,Pilania, Meenakshi,Shekar, K.P. Chandra
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p. 831 - 836
(2013/06/05)
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- Sulfonylation of aromatic compounds with methyl p-toluenesulfonate as a sulfonylating precursor
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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
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p. 507 - 512
(2013/02/22)
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- Novel C-H functionalization of arenes: Palladium-catalyzed synthesis of diaryl sulfides
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A novel protocol for the direct arylthiolation of electron-rich arenes is described. Applying arylsulfonyl cyanides in the presence of catalytic amounts of Pd allows for a straightforward synthesis of diaryl sulfides.
- Anbarasan, Pazhamalai,Neumann, Helfried,Beller, Matthias
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supporting information; experimental part
p. 3233 - 3235
(2011/05/05)
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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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- Highly selective catalytic Friedel-Crafts sulfonylation of aromatic compounds using a FeCl3-based ionic liquid
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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
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p. 3931 - 3934
(2008/09/21)
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- Rapid and mild sulfonylation of aromatic compounds with sulfonic acids via mixed anhydrides using Tf2O
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An efficient and direct sulfonylation of aromatic compounds with sulfonic acids is described via mixed anhydrides in short reaction times using Tf2O in nitromethane at room temperature.
- Alizadeh, Abdolhamid,Khodaei, Mohammd Mehdi,Nazari, Ehsan
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p. 6805 - 6808
(2008/03/12)
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- Highly selective catalytic Friedel-Crafts acylation and sulfonylation of activated aromatic compounds using indium metal
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The Friedel-Crafts acylation of activated benzenes with various aromatic and aliphatic acid chlorides was studied in the presence of indium metal. The reaction was accomplished in high isolated yields under solvent or solvent-less conditions. The method is also applicable for preparing diaryl sulfones from aromatic compounds and aryl sulfonyl chlorides.
- Jang, Doo Ok,Moon, Kyung Soo,Cho, Dae Hyan,Kim, Joong-Gon
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p. 6063 - 6066
(2007/10/03)
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- Direct sulfonylation of aromatic rings with aryl or alkyl sulfonic acid using supported P2O5/Al2O3
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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
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p. 2029 - 2034
(2007/10/03)
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- Fe-pillared bentonite-an efficient catalyst for sulfonylation of arenes using aryl and alkyl sulfonyl chlorides
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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.
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p. 9079 - 9082
(2007/10/03)
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- An efficient and convenient method for the synthesis of aromatic sulfones catalysed by ZrO2/S2O82- solid superacid
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A manipulatively simple and rapid procedure for the synthesis of diaryl sulfones from arylsulfonyl chlorides with aromatic compounds is described; the reaction is conducted under Friedel-Crafts conditions in the absence of solvent using ZrO2/S2O82- as catalyst in 78-93% yields.
- Jin, Tongshou,Yang, Mina,Feng, Guoliang,Li, Tongshuang
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p. 721 - 723
(2007/10/03)
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- Magnesium perchlorate: An efficient catalyst for selective sulfonylation of arenes under neutral conditions
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Magnesium perchlorate is found to be an extremely efficient catalyst for the sulfonylation of activated, unactivated and heterocyclic aromatics under almost neutral conditions.
- Bandgar,Kamble,Bavikar
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p. 287 - 289
(2007/10/03)
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- Synthesis of sulfones using sodium perchlorate as a catalyst under neutral conditions
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Sulfonylation of aromatics with p-toluenesulfonyl chloride in the presence of a catalytic amount of sodium perchlorate gives the corresponding sulfones. Selectivity and neutral condition are the attractive features of this methodology.
- Bandgar,Kamble,Fulse,Deshmukh
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p. 1105 - 1107
(2007/10/03)
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- Selective sulfonylation of arenes and benzoylation of alcohols using lithium perchlorate as a catalyst under neutral conditions
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Sulfonylation of aromatics with p-toluenesulfonyl chloride and benzoylation of alcohols with benzoyl chloride using lithium perchlorate as a catalyst is described. The remarkable selectivity under neutral conditions is an attractive feature of this method.
- Bandgar,Kamble,Sadavarte,Uppalla
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p. 735 - 738
(2007/10/03)
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- Sodium periodate catalyzed selective sulfonylation of aromatics
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Sodium periodate catalyzed sulfonylation of aromatics with p-toluenesulfonyl chloride gives the corresponding sulfones in good yield under neutral conditions.
- Bandgar,Kamble
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p. 1066 - 1067
(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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- Friedel - Crafts sulfonylation in 1-Butyl-3-methylimidazolium chloroaluminate ionic liquids
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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
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p. 8616 - 8620
(2007/10/03)
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- Indium-catalysed aryl and alkyl sulfonylation of aromatics
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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
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p. 830 - 832
(2007/10/03)
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- Zinc-mediated fast sulfonylation of aromatics
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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
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p. 1065 - 1068
(2007/10/03)
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- Friedel-Crafts sulfonylation of aromatics catalysed by solid acids: An eco-friendly route for sulfone synthesis
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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
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p. 2689 - 2693
(2007/10/03)
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- Fe(III) exchanged montmorillonite: A mild and ecofriendly catalyst for sulfonylation of aromatics
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Fe(III) exchanged montmorillonite clay catalyses Friedel-Crafts sulfonylation of arenes with arylsulfonyl chlorides to obtain the corresponding sulfones in excellent yields.
- Choudary,Chowdari, N. Sreenivasa,Kantam, M. Lakshmi,Kannan
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p. 2859 - 2862
(2007/10/03)
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- Formation of 2-arylnaphthalenes from N-tosylated phenylalanine derivatives
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N-Tosylated phenylalanine derivatives in benzene in the presence of sulfuric acid afforded 2-arylnaphthalene derivatives in moderate yields. The reaction might proceed via the corresponding decarbonylated N-tosylimine derivatives. Aldol type reaction of N-tosylimines followed by intramolecular Friedel-Crafts reaction and elimination of p-toluenesulfonamide gave 2- arylnaphthalenes.
- Seong, Mi Ra,Song, Hyun Nam,Kim, Jae Nyoung
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p. 7101 - 7104
(2007/10/03)
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