- Visible-light-driven electron donor-acceptor complex induced sulfonylation of diazonium salts with sulfinates
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This work reports an efficient sulfonylation reaction enabled by a visible-light-induced radical coupling reaction between phenyl/heterocyclic diazonium salts and sulfinates. Mechanistic experiments disclosed the formation of a versatile electron donor-acceptor (EDA) complex. This transformation is characterized by an easy operational procedure under mild conditions which avoids transition metals, ligands, catalysts, and oxidants.
- Cheng, Lan,Guo, Jianbo,Li, Yufei,Liang, Xin,Wang, Qingmin,Xia, Qing,Zhang, Pei,Zhang, Weihua
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supporting information
p. 8865 - 8870
(2021/11/30)
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- Method for synthesizing sulfone compounds under photocatalysis condition
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The invention belongs to the technical field of compound preparation, and particularly relates to a method for synthesizing sulfone compounds under a photocatalysis condition. Aromatic hydrazine and sulfinate are used as raw materials, and under the action of alkali and a solvent, a sulfone compound is generated through reaction under the condition of air or oxygen under the illumination of visible light. According to the method disclosed by the invention, aryl hydrazine is used as an arylation reagent, polyacid salt is used as a catalyst or an organic photosensitizer is used as a catalyst, and the sulfones compound can be efficiently synthesized by coupling with sulfinate under the condition of room temperature through visible light irradiation. The method has good substrate universalityand relatively mild reaction conditions, is not only a substitute for synthesizing sulfone compounds by coupling from simple substrates reported at present, but also broadens the new application of the polyacid salt in the field of photocatalysis.
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Paragraph 0159-0163
(2021/03/31)
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- Mo(VI) complex catalysed synthesis of sulfonees and their modification for anti-HIV activities
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An efficient method for the synthesis of sulfones has been developed using sugar derived cis-dioxo molybdenum(VI) complex as catalyst and urea hydrogen peroxide as oxygen source. Present method is highly specific for sulfide oxidation irrespective of presence of alkene and aldehyde groups in the same molecule. Synthesis of fifteen sulfones have been reported with 82–98% isolated yields and the catalyst has been reused five times without any loss in its activity. 2-(Phenylsulfonyl)aniline has been condensed with eight different aromatic aldehydes and the products are being explored for HIV-1 reverse transcriptase inhibition activities.
- Madduluri, Vimal Kumar,Baig, Noorullah,Chander, Subhash,Murugesan, Sankaranarayanan,Sah, Ajay K.
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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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- 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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- Organic photoredox catalysis enabled cross-coupling of arenediazonium and sulfinate salts: Synthesis of (un)symmetrical diaryl/alkyl aryl sulfones
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We disclose herein the first transition-metal-and external oxidant/reductant-free visible-light-mediated synthesis of (un)symmetrical diaryl/alkyl aryl sulfones from arenediazonium tetrafluoroborates and sodium sulfinates using eosin Y as an organic photoredox catalyst. The utilization of visible light as an inexpensive and ecosustainable energy source, operational simplicity, ambient temperature and clean reaction in aqueous acetonitrile are the salient features of the developed protocol. The desired sulfones were also synthesized via a one-pot, two-step process directly from anilines and sulfinate salts in good to excellent yields.
- Chawla, Ruchi,Yadav, Lal Dhar S.
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supporting information
p. 4761 - 4766
(2019/05/24)
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- A Convenient Synthesis of Sulfones via Light Promoted Coupling of Sodium Sulfinates and Aryl Halides
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A convenient and e?cient synthesis of sulfones from sulfinates and aryl halides was developed. The reaction occurred under UV irradiation without transition metal catalyst or photocatalyst. A radical pathway via single-electron transfer (SET) of electron donor-acceptor (EDA) complex was proposed based on UV-vis spectroscopy, radical inhibiting and trapping experiments. (Figure presented.).
- Chen, Lei,Liang, Jie,Chen, Zhen-yu,Chen, Jie,Yan, Ming,Zhang, Xue-jing
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p. 956 - 960
(2019/01/25)
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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 catalyzed synthesis of unsymmetrical diaryl sulfones from an arenediazonium salt and sodium p-toluenesulfinate
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Aryl sulfones have been for the first time synthesized by the reaction of sodium p-toluenesulfinate and arenediazonium salts using a CuI catalyzed homogeneous system. The developed protocol is a simple and efficient new route for the synthesis of diaryl sulfones with excellent product yields. The mild reaction conditions tolerate a range of functional groups. The best results were obtained with CuI, N,N′-dimethylethylenediamine, TBAI and K2CO3 in dimethyl sulfoxide at 100°C under an inert atmosphere.
- Gund, Sitaram Haribhau,Shelkar, Radheshyam Suresh,Nagarkar, Jayashree Milind
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p. 62926 - 62930
(2015/08/06)
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- First palladium-catalyzed denitrated coupling of nitroarenes with sulfinates
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The first example of palladium-catalyzed protocol for the denitrated coupling of nitroarenes with sulfinates was developed, achieving aryl and heterocyclic sulfones in moderate to excellent yields. The cyclopalladated ferrocenylimine (I) exhibited highly catalytic activity for this transformation with low catalyst loading (0.75 mol %). The efficiency of this reaction was demonstrated by compatibility with a wide range of groups. Thus, the method represents a simple and facile procedure to access aryl and heterocyclic sulfones.
- Tian, Heng,Cao, Aijuan,Qiao, Lijun,Yu, Ajuan,Chang, Junbiao,Wu, Yangjie
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supporting information
p. 9107 - 9112
(2015/03/05)
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- Magnetically separable copper ferrite nanoparticles-catalyzed synthesis of diaryl, alkyl/aryl sulfones from arylsulfinic acid salts and organohalides/boronic acids
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A recyclable, inexpensive, non-toxic and environmentally benign catalytic system comprised of magnetically separable copper ferrite (CuFe 2O4) nanoparticles has been developed for the synthesis of diaryl, alkyl/aryl sulfones. Arylsulfinic acid salts are coupled with various alkyl/aryl halides/boronic acids to afford the corresponding diaryl, alkyl/aryl sulfones in good to excellent yields under the identical catalytic system. A wide range of functional group tolerance, with facile recovery of the catalyst by application of an external magnetic field, and consistently high catalytic efficiency for five consecutive cycles render the protocol operationally attractive.
- Srinivas,Rawat, Vikas S.,Konda, Kavitha,Sreedhar, Bojja
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p. 805 - 817
(2014/04/03)
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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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- Palladium-catalyzed aromatic sulfonylation: A new catalytic domino process exploiting in situ generated sulfinate anions
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Allylic sulfones are excellent precursors of aryl sulfones via a new Pd-catalyzed domino sequence involving in situ generation of sulfinate anions and subsequent cross-coupling with aryl -iodides or bromides. Georg Thieme Verlag Stuttgart · New York.
- Le Duc, Ga?tan,Bernoud, Elise,Prestat, Guillaume,Cacchi, Sandro,Fabrizi, Giancarlo,Iazzetti, Antonia,Madec, David,Poli, Giovanni
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supporting information; experimental part
p. 2943 - 2946
(2012/01/05)
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- New sources of "active" halogen bis(dialkylamide)hydrogen dibromobromates, efficient reagents for destruction of ecotoxicants
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Bis(dialkylamide)hydrogen dibromobromates were synthesized and their reactivity was investigated in decomposition of diethylphosphonic, diethylphosphoric, and 4-toluenesulfonic acids 4-nitrophenyl esters. The nucleophilic reactivity of a typical α-nucleop
- Prokop'eva,Mikhailov,Turovskaya,Karpichev,Burakov,Savelova,Kapitanov,Popov
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experimental part
p. 637 - 646
(2009/04/10)
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- Rapid and highly chemoselective biomimetic oxidation of organosulfur compounds with tetrabutylammonium peroxymonosulfate in the presence of manganese meso-tetraphenylporphyrin and imidazole
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A novel and efficient method is described for the immediate oxidation of different organosulfur compounds using tetrabutylammonium peroxymonosulfate in the presence of manganese meso-tetraphenylporphyrin and imidazole. The method is highly chemoselective and the yields are excellent.
- Iranpoor, Nasser,Mohajer, Daryoush,Rezaeifard, Abdol-Reza
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p. 3811 - 3815
(2007/10/03)
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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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- 5-arylsulfonyl indoles useful for treating disease
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The invention provides derivatives of 5-arylsulfonyl indole and 5-arylsulfonyl indoline compounds which may be in the form of pharmaceutical acceptable salts or compositions that are useful in treating central nervous system diseases such as anxiety and depression. The invention also includes intermediates and processes to make the compounds, isotopically-labeled forms of the compounds and the use of the isotopically labeled forms of the compounds to perform nuclear magnetic resonance imaging and positron emission tomography.
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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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- Caro's acid supported on silica gel. IV. Facile synthesis of sulfones by the oxidation of various sulfides in aprotic solvent
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Oxidation of sulfides with Caro's acid supported on silica gel in acetonitrile gave sulfones in high to excellent yields under mild condition.
- Lakouraj, Moslem M.,Movassagh,Ghodrati
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p. 847 - 850
(2007/10/03)
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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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- A CHEMICAL AND THERMOCHEMICAL STUDY OF NON-OBSERVED SYMMETRY ALLOWED REACTIONS
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A variety of reactions, whilst predicted to be symmetry allowed, are not observed experimentally.Several such non-observed yet allowed reactions have been studied in order to understand them and to possibly bring about, with suitably modified substrates, their observation.For example, although ozone adds to ?-bonds, the isoelectronic nitro group does not, due to a high activation energy barrier.This reaction is of the type ABC.Molecular orbital calculations of a series of 1,3-dipolar species reveal a correlation of the ? bond order with their effectiveness in -additions.Based on this, the nitro group as well as ozone should be considered as poor dipolar agents.The exceptionally high ΔHof of ozone (+34.00 kcal mol-1) as compared with that of nitrobenzene (+3.8 kcal mol-1) could possibly explain the reactivity of the former.This is reflected in an estimated ΔHo value of -45.5 kcal mol-1 for the ethylene-ozone addition as compared with +7.5 kcal mol-1 for the non-occuring ethylene-nitrobenzene addition.Thermochemical calculations demonstrate that the nitrogroup is more prone to undergo addion as a 2? partner than as a 1,3-dipolar reagent.The thermal, nitro group-olefin addition has been examined using a variety of electrophilic nitrobenzenes with tetracyclone as the common substrate.The extent of cyclo-addition was assessed on the basis of the isolation of 2-benzoyl-3,4,5-triphenylfuran. 4-Nitro-4'-methyl diphenyl sulfone and 4,4'-dinitro diphenyl sulfone have been identified as efficient reagents for these reactions.The former compound has been found to add to even non-conjugated olefins.The clean thermal transformation of crystalline 7,7-dimethyl-bicycloheptane-1-nitrile oxide to the corresponding isocyanate is an example of the observable ABC change.In this case, the oxazirine corresponding to B, arising from conrotatory cyclisation, undergoes irreversible rupture (BC).Such transformations are not observed with the stereochemically more favoured nitrones since these belong to the type AB.The ?4s+?2s addition of carboxylates to olefins would lead to a carbon base at the expense of an oxygen one.This is clearly unfavourable and is not observed.On the other hand, the reverse of this reaction, namely , the fragmentation of ketal conjugate bases to carboxylates would be expected to be facile.This is indeed so and the process has been shown to be concerted.Ketals from p-nitrobenzaldehyde are shown to undergo fragmentation with 1,5-diazabicyclononene-5 (DBN) to olefins.The carboxylate-olefin addition belongs to the general category ?+A-B-, that encompasses cycloadditions, electrocyclic reactions and sigmatropic shifts.An equation ΔG deg=BHa-pKAHa)+X>kcal mol-1, wherein X is dependent on the reaction type has been derived for predicting the ΔGo for these ?+AB processes.Of practical interest is the development of perturbed ?+A1B1 systems that are predicted to occur in the forward direction, where the parent type ...
- Ranganathan, S.,Ranganathan, D.,Ramachandran, P. V.,Mahanty, M. K.,Bamezai, S.
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p. 4171 - 4184
(2007/10/02)
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