- Synthesis of Substituted Pyrroles via Copper-Catalyzed Cyclization of Ethyl Allenoates with Activated Isocyanides
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A new method for the synthesis of di- and trisubstituted pyrroles via copper-catalyzed cyclization of ethyl allenoates with activated isocyanides has been developed. In contrast to related annulation reactions previously reported, this new process features a skeletal rearrangement in which the aryl sulfonyl moiety, which functions as the electron-withdrawing group in the α-carbon of the isocyanide, was found to migrate to the γ-carbon of the starting allenoate in the final product for the first time.
- Lu, Kui,Ding, Fang,Qin, Long,Jia, Xiaoliang,Xu, Chuanming,Zhao, Xia,Yao, Qingwei,Yu, Peng
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- Reduction of Sulfonic Acids and Related Organosulfur Compounds with Triphenylphosphine-Iodine System
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Arenesulfonic acids, their sodium salts, and alkyl arenesulfonates can be reduced readily to the corresponding arenethiols quantitatively by treatment with a mixture of triphenylphosphine and a catalytic amount of iodine, while alkanesulfonic acids, sulfinic acids, disulfides, thiosulfonic S-esters, and sulfonates are also readily reduced to the corresponding thiols similarly.Upon treatment with a mixture of triphenylphosphine and excess iodine, however, these aliphatic sulfur compounds are converted eventually to the corresponding alkyl iodides.The relative reactivities of these sulfonyl derivatives in the reaction with the triphenylphosphine-iodine system are the following.Aromatic series: ArSO2Cl, ArSO2SAr' > ArSO2H > ArSO3R > ArSO3-HNBu3+ (or PyH+) > ArSO3H > ArSO2SO2Ar >> ArSO2CH2C(CH3)3, ArSO3Ar'.Aliphatic series: RSO2Cl, RSO2SR', RSO2-HNBu3+ > RSO3-HNBu3+ > RSSR, RSO2H > RSO3H > RSH > RSO3R'.In these reactions, the arenesulfonic acids bearing electron-donating substituents can be reduced more readily than those having electron-withdrawing substituents.
- Oae, Shigeru,Togo, Hideo
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- Photoredox Catalyzed Sulfonylation of Multisubstituted Allenes with Ru(bpy)3Cl2 or Rhodamine B
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A highly regio- and stereoselective sulfonylation of allenes was developed that provided direct access to α, β-substituted unsaturated sulfone. By means of visible-light photoredox catalysis, the free radicals produced by p-toluenesulfonic acid reacted with multisubstituted allenes to obtain Markovnikov-type vinyl sulfones with Ru(bpy)3Cl2 or Rhodamine B as photocatalyst. The yield of this reaction could reach up to 91%. A series of unsaturated sulfones would be used for further transformation to some valuable compounds.
- Chen, Jingyun,Chen, Shufang,Jiang, Jun,Lu, Qianqian,Shi, Liyang,Xu, Zekun,Yimei, Zhao
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supporting information
(2021/11/09)
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- tert-Butyl Hydroperoxide-Initiated Radical Cyclization of 1-(Allyloxy)-2-(1-Arylvinyl)Benzenes with Sulfinic Acids to Access Sulfonated Benzoxepines
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A tert-butyl hydroperoxide-initiated radical cyclization of 1-(allyloxy)-2-(1-arylvinyl)benzenes with sulfinic acids for the construction of sulfonated benzoxepines is developed. This reaction involves a radical pathway and offers a straightforward route to the formation of seven-membered ring via sulfonylation/cyclization process. This methodology features mild reaction conditions, a broad substrate scope and good functional group tolerance. (Figure presented.).
- Kuang, Kaimo,Wu, Meixia,Wu, Sixin,Xia, Ziqin,Xu, Qiankun,Zhang, Man,Zhou, Nengneng
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supporting information
p. 3491 - 3495
(2021/06/28)
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- Visible-Light-Induced Radical Cascade Cyclizations of 1,7-Enynes with Sulfinic Acids: Direct Access to Sulfonated Chromanes and Sulfonated Tetrahydroquinolines under Metal-Free Conditions
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Visible-light-induced strategy to access sulfonated chromanes and sulfonated 1,2,3,4-tetrahydroquinolines via a radical cascade cyclization of 1-(arylethynyl)-2-(vinyloxy)benzenes and N-allyl-2-(arylethynyl)anilines with aromatic and aliphatic sulfinic acids has been developed. In the presence of TBHP (7.5 mol%) as an oxidant and Eosin Y (3.0 mol%) as a photocatalyst, the reactions undergo smoothly to afford the corresponding products in good yields at room temperature under metal-free conditions. This transformation features low loading of TBHP, mild reaction conditions, simple operation, broad functional-group tolerance, and good yields of products. (Figure presented.).
- Liu, Qi,Mei, Yousheng,Wang, Lei,Ma, Yongmin,Li, Pinhua
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supporting information
p. 5669 - 5680
(2020/10/28)
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- Synergistic combination of visible-light photo-catalytic electron and energy transfer facilitating multicomponent synthesis of β-functionalized α,α-diarylethylamines
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A synthetic strategy with the visible-light photo-catalytic synergistic combination of electron and energy transfer processes has been developed. The mild reaction conditions allow the radical-radical cross-coupling phenomenon for the multicomponent synthesis of β-arylsulfonyl(diarylphosphinoyl)-α,α-diarylethyl-amines from readily available arylsulfinic acids (diarylphosphine oxides), 1,1-diarylethylenes and arylazides.
- Wu, Yanan,Zhang, Yipin,Jiang, Mingjie,Dong, Xunqing,Jalani, Hitesh B.,Li, Guigen,Lu, Hongjian
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p. 6405 - 6408
(2019/06/07)
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- Direct Substitution of Secondary and Tertiary Alcohols to Generate Sulfones under Catalyst- and Additive-Free Conditions
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An environmentally benign protocol that affords propargylic sulfones containing highly congested carbon centers from easily accessible alcohols and sulfinic acids with water as the only byproduct is reported. The reaction proceeded via an in situ dehydrative cross-coupling process by taking advantage of the synergetic actions of multiple hydrogen bonds rather than relying on an external catalyst and/or additives to achieve high product distribution.
- Liu, Yanan,Xie, Peizhong,Sun, Zuolian,Wo, Xiangyang,Gao, Cuiqing,Fu, Weishan,Loh, Teck-Peng
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supporting information
p. 5353 - 5356
(2018/09/13)
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- Tert-Butyl Nitrite Promoted Oxidative Intermolecular Sulfonamination of Alkynes to Synthesize Substituted Sulfonyl Pyrroles from the Alkynylamines and Sulfinic Acids
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tert-Butyl nitrite promoted oxidative intermolecular sulfonamination of alkynes to synthesize substituted sulfonyl pyrroles from the alkynylamines and sulfinic acids via tandem addition/cyclization was developed. This reaction is performed well by employing tert-butyl nitrite as the oxidant, and various substituted sulfonyl pyrroles are formed in moderate to good yields with no requirement of metal catalysis.
- Qi, Zhenjie,Jiang, Yong,Wang, Yanyan,Yan, Rulong
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p. 8636 - 8644
(2018/06/18)
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- Method for synthesizing aryl sulfonic acid by utilizing sulfur dioxide
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The invention relates to a method for synthesizing aryl sulfonic acid by utilizing sulfur dioxide. The method is characterized by comprising the following steps that S1, aromatic hydrocarbon is added into a solvent, stirring is performed to achieve complete dissolution, and then a catalyst is added; S2, under the stirring condition and the conditions of 0-100 DEG C and 0-10 atm, dried excessive sulfur dioxide gas or sulfur dioxide liquid are added, and reaction is performed for 0.5-50 hours; S3, the reaction liquid obtained in the step S2 is cooled to 10 DEG C or below, pressurized filtration is performed, and a catalyst is recovered; S4, filtrate is distilled to recover unreacted sulfur dioxide, then the solvent is recovered through distillation, the residual solid is the product aryl sulfonic acid, and the product yield is higher than 85%. The raw materials for the method for synthesizing the aryl sulfonic acid by utilizing the sulfur dioxide are cheap and easy to obtain, the product yield is high, the production process is safer, ad the severe environmental pollution of a traditional process is greatly reduced.
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Paragraph 0042-0047; 0066-0070
(2018/01/04)
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- Visible-Light Photocatalytic Bicyclization of 1,7-Enynes toward Functionalized Sulfone-Containing Benzo[a]fluoren-5-ones
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A new visible-light photocatalytic arylsulfonylation and bicyclization of C(sp3)-tethered 1,7-enynes with sulfinic acids has been developed, delivering functionalized sulfone-containing benzo[a]fluoren-5-ones with generally good yields. This Eosin Y-catalyzed approach makes use of visible light as a safe and eco-friendly energy source to drive cascade cyclization reactions, resulting in continuous multiple bond-forming events including C–S and C–C bonds to efficiently construct polycyclic-linked alkyl aryl sulfones. (Figure presented.).
- Huang, Min-Hua,Zhu, Yi-Long,Hao, Wen-Juan,Wang, Ai-Fang,Wang, De-Cai,Liu, Feng,Wei, Ping,Tu, Shu-Jiang,Jiang, Bo
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supporting information
p. 2229 - 2234
(2017/07/07)
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- Copper-mediated cascade synthesis of diaryl sulfones via the sandmeyer reaction
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A convenient and efficient method for the copper-mediated cascade synthesis of diaryl sulfones via the Sandmeyer reaction has been developed. The protocol uses readily available aryl amines and arylsulfinic acids as the starting materials, isoamyl nitrite as the diazotizating reagent of the aryl amines, and the method shows mild reaction conditions and high tolerance towards various functional groups in the substrates. Georg Thieme Verlag Stuttgart New York.
- Yang, Xiaobo,Shi, Liangliang,Fu, Hua
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supporting information
p. 847 - 852
(2014/04/17)
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- Three-component reactions of ketene dithioacetals, aldehydes, and arenesulfinic acids: Facile synthesis of allylic sulfones
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A facile and efficient synthesis of allylic sulfones via sulfuric acid-mediated three-component reactions of easily available ketene dithioacetals, aldehydes, and arenesulfinic acids is presented. The reaction features low cost and good yields.
- Liang, Deqiang,Huang, Wenzhong,Yuan, Lin,Ma, Yinhai,Ouyang, Liping,Rao, Yuqin,Yang, Yuxian
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supporting information
p. 1930 - 1937
(2014/07/07)
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- Microwave-accelerated Pd-catalyzed desulfitative direct C2-arylation of free (NH)-indoles with arylsulfinic acids
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The rapid and efficient direct C2-arylation of free (NH)-indoles with arylsulfinic acids proceeded through a microwave-accelerated palladium-catalyzed desulfitation reaction. By using PdCl2 as a catalyst, silver acetate as an oxidant, and H2SO4 as an additive, arylsulfinic acids with both electron-donating and electron-withdrawing groups underwent desulfitative coupling with an array of free (NH)-indoles, thereby selectively providing C2-arylindoles in good yields. From C2 shining sea: The direct C2-arylation of free (NH)-indoles with arylsulfinic acids proceeded through a Pd-catalyzed desulfitation reaction. In the presence of an oxidant and an additive, 2-arylindoles were selectively afforded in good yields. Copyright
- Miao, Tao,Li, Pinhua,Wang, Guan-Wu,Wang, Lei
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p. 3185 - 3190
(2014/01/06)
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- Palladium-catalyzed desulfitative heck-type reaction of aryl sulfinic acids with alkenes
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An efficient protocol has been developed for the desulfitative Heck-type reaction of aryl sulfinic acids with a variety of alkenes in the presence of a catalytic amount of Pd(OAc)2 and inexpensive Cu(OAc)2 as oxidant. This method does not require a ligand or a base, thereby broadening the scope of Pd-catalyzed coupling reactions. Copyright
- Wang, Guan-Wu,Miao, Tao
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supporting information; experimental part
p. 5787 - 5790
(2011/06/23)
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- Synthesis of ketones by palladium-catalysed desulfitative reaction of arylsulfinic acids with nitriles
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Palladium-catalysed desulfitative addition of arylsulfinic acids to aryl and alkyl nitriles with 2,2′-bipyridine as a ligand afforded a variety of aryl ketones via hydrolysis of ketimine intermediates.
- Miao, Tao,Wang, Guan-Wu
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supporting information; experimental part
p. 9501 - 9503
(2011/10/01)
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- Catalyst-free alkylation of sulfinic acids with sulfonamides via sp 3 C-N bond cleavage at room temperature
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An unprecedented catalyst-free alkylation of sulfinic acids with sulfonamides has been developed via sp3 C-N bond cleavage at room temperature. In the absence of external catalysts and additives, a wide variety of N-benzylic and N-allylic sulfonamides couple with sulfinic acids to give structurally diversified sulfones in moderate to excellent yields. Furthermore, the reaction of N-(2-acyl)allylic sulfonamides with sulfinic acids provides a convenient access to trisubstituted allyl sulfones with exclusive Z selectivity.
- Liu, Cong-Rong,Li, Man-Bo,Cheng, Dao-Juan,Yang, Cui-Feng,Tian, Shi-Kai
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supporting information; experimental part
p. 2543 - 2545
(2009/10/10)
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- Kinetics and mechanisms of the acid-catalyzed hydrolyses of N-(4-substituted-arylsulfinyl)phthalimides
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The acid-catalyzed hydrolyses of N-(4-substituted-arylsulfinyl)phthalimides were studied in aqueous solutions of perchloric and sulfuric acids at 50.0 ± 0.1 and of hydrochloric acid at 40.0 ± 0.1°C. Analysis of the data by the Cox-Yates excess acidity method and substituent, temperature and solvent isotope effects indicate hydrolysis by an A2 mechanism at low acidity. At higher acidities a changeover to an A1 mechanism is observed. Copyright
- Kutuk, Halil,Bekdemir, Yunus,Soydas, Yasemin
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p. 224 - 228
(2007/10/03)
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- Kinetics of the Reaction of 2,4-Dinitrophenyl-4'-substituted Phenyl Sulfones with Morpholine in Methanol
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The rates of morpholine-desulfonylation of 2,4-dinitrophenyl-4'-substituted phenylsulfones (1-6: aryl = 4-Y-C6H4, Y = H, CH3, OCH3, Br, Cl and NO2) have been measured in methanol at different temperatures (25 deg C-40 deg C) and the activation parameters were calculated.A good Hammett correlation was obtained with ρ values of 0.43-0.75.The plot ΔH(excit.) versus ΔS(excit.) gave an isokinetic temperature at 339 deg K.
- El-Mallah, Nabila M.,Hamed, E. A.,El-Bardan, A. A.
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p. 319 - 328
(2007/10/03)
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- Nitrosations with hydrazine derivatives: Synthesis of N4-arenesulfinylsemicarbazides and N5-arenesulfinyl-N1-aminobiuretes from arenesulfinylisocyanates and N,N-disubstituted hydrazines
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Arenesulfinyl-isocyanates 5 prepared in situ from arenesulfinyl chlorides 4 and silver cyanate react with N,N-disubstituted hydrazines to mixtures of N4-arenesulfinylsemicarbazides 6 as main components and N5-arenesulfinyl-N1/s
- Hanefeld,Landwehr
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p. 344 - 351
(2007/10/02)
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- Convenient methods for the preparation of sulfur substituted allenecarboxylates
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2-Sulfinyl- and 2-sulfonylallenecarboxylates, as new 1,1-diacceptor substituted allenes, were prepared starting from methyl 4-hydroxy-4-methyl-2-pentynoate by a [2,3]-sigmatropic rearrangement. The sulfoxides could be reduced to the corresponding allenyl sulfides. A 2(5H)-furanone derivative was prepared by a side-reaction.
- Conrads,Mattay
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- Sulfinic Acids and Related Compounds 23. Preparation of Sulfinic Acids by the Reaction of Sulfonyl Halides with Thiols
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The reaction of arene- and alkanesulfonyl halides with p-thiocresol in the presence of triethylamine at -76 deg C gives triethylammonium sulfinates, which after acidification afford sulfinic acids of 95 - 100 percent purity in yields of 51 - 92 percent for 18 typical representatives.The synthesis succeeds in certain instances where conventional reduction with aqueous sodium sulfite fails and in other instances often is superior.The method is rapid, mild, selective, convenient, and general, although a few limitations are reported.Characterizations of the sulfinic acids are effected by titration with aqueous sodium nitrite, by IR and 1H-NMR spectra, by preparation of either a S-benzylthiuronium salt or a p-nitrobenzyl ester and either by elemental analyses or comparison with reported melting points of the acids and derivatives as appropriate.
- Lee, Chew,Field, Lamar
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p. 391 - 397
(2007/10/02)
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- A Novel Synthesis of Aromatic Sulfinic Acids
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Aromatic sulfinic acids were synthesized conveniently by the direct oxidation of thiols with 30percent aqueous hydrogen peroxide at room temperature in good yield.Keywords - oxidation; thiol; sulfinic acid; benzene sulfinic acid; hydrogen peroxide.
- Kamiyama, Tsutomu,Enomoto, Saburo,Inoue, Masami
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p. 2652 - 2653
(2007/10/02)
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- MODERN FRIEDEL-CRAFTS CHEMISTRY. XIV. ON THE CYCLIZATION OF SELECTED ARYL HYDROXYALKYL SULFIDES
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The feasibility of cycloalkylation reactions in the presence of Friedel-Crafts catalysts was demonstrated in a nimber of aryl hydroxyalkyl sulfides (1-5), and benzyl hydroxyalkyl sulfides (6-7).Treatment of compounds (1-7) with Friedel-Crafts catalysts gave diaryl disulfides, diaryl sulfides, arene thiols, chlorohydrins, aryl chloroalkyl sulfides, aryl alkenyl sulfides and cyclization products.It is noteworthy to mention that cyclization products were isolated only in cases where the hydroxyl group is linked to a tertiary carbon atom as in compounds 3 and 7.A suitable reaction pathway is suggested to rationalize the formation of the various reaction products.
- El-Khawaga, A. M.,El-Zohry, M. F.,Ismail, M. T.,Abdel-Wahab, A. A.,Khalaf, A. A.
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p. 265 - 270
(2007/10/02)
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- ELECTRON-TRANSFER PROCESSES: SULPHENYLATION OF ELECTRON-RICH SYSTEMS BY DIARYL DISULPHIDES AND ARYLTHIOSULPHONATES
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Diphenyl disulphide, 1, reacts with 1-methyl-2-phenylindolizine, 2, in refluxing ethanol furnishing sulphenylation; dibenzothiazolyl disulphide, 6, a compound with a low S-S bond energy reacts with the isomers 1-methyl-2-phenylindolizine, 2, and 3-methyl-2-phenylindolizine, 3, at room temperature in high yields. 2-Phenylindole, 4, 1-methyl-2-phenylindole, 5, and some of their 3-substituted derivatives, which have an higher oxidation potential than indolizines, react with diphenyl disulphide only under irradiation.The sulphenylation of these substrates can be easily obtained either by metal activation or using dibenzothiazolyl disulphide, 6.Arylthiosulphonates sulphenylate indole and indolizine derivatives at room temperature.On the basis of reaction products and ESR evidence, all these reactions are discussed in terms of electron-transfer processes.
- Berti, Corrado,Colonna, Martino,Poloni, Marino
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p. 181 - 184
(2007/10/02)
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- STUDIEN ZUM VORGANG DER WASSERSTOFFUEBERTRAGUNG.61. Chemische Reaktivitaet und Halbstufenpotential Vergleichende Versuche am Beispiel einiger Arylsulfonsaeurederivate
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In arylsulfonyl halides, the half-wave potentials of the corresponding chlorides and fluorides differ by more than 1000 mV, the fluoride being more negative; the influence of para-substituents is small for the chlorides, large for the fluorides.In agreement with the half-wave potentials, arylsulfonyl chlorides are considerably more reactive chemically than the corresponding fluorides.The O-selectivity found for P(O)F compounds is not observed in arylsulfonyl fluorides.Studies of competitive ester formation using primary and secondary alcohols and various arylsulfonyl chlorides yielded no clear analogy to the half-wave potentials.The primary alcohol is always sulfonated in preference to the secondary alcohol, whether the hydroxy functions are present in different molecules or the same molecule.In the latter case, the secondary hydroxyl function is then attacked in a further step by a second, different, arylsulfonyl chloride, giving the compounds 4-8.The further electroreduction of these diesters may be carried out in high yields, giving selective fission of one ester linkage only (that with the more positive potential) provided the difference in the half-wave potentials of the different ester linkages is sufficiently large.In the electroreductive fission the monosulfinic acid and the corresponding alcohol are liberated (see table II).In the competition reaction between phenol and 1:1 mixtures of tosyl chloride (A) and p-carboxyethyl-benzenesulfonyl chloride (B), the chloride with the more positive potential (B), E1/2=72 mV reacts quicker by a factor of 2.5.In competitive Finkelstein reactions, the selectivity was 1:11 at a difference in half-wave potentials of 760 mV (table IV).Arylsulfonates with free secondary alcohol functions may be oxidized smoothly and in high yield to the corresponding ketone using Na2Cr2O7 (3), without effecting the sulfonate linkage.The alkali hydrolysis of n-hexyl para-substituted arylsulfonates follows the Hammett relation but shows a lesser selectivity than was observed in the electroreductive fission of the same esters at the required potentials.Tables VI, VII and VIII concentrate on the preparative importance of the potential-controlled electroreductive fission of aliphatic and aromatic arylsulfonates.The corresponding hydroxy compounds are liberated in yields of up to over 90percent: N-alkyl- and N-aryl arylsulfonamides give analogous results. (table IX)
- Horner, Leopold,Schmitt, Rolf-Erhard
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p. 189 - 212
(2007/10/02)
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- STUDIEN ZUM VORGANG DER WASSERSTOFFUEBERTRAGUNG 64. ELECTROREDUCTIVE SPALTUNG VON ARYLSULFONSAEUREDERIVATEN UND ARYLSULFONEN MIT ALKALI-AMALGAMEN
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Arylsulfonylchlorides, n-hexylarylsulfonates and di-aryl sulfones (ArSO2Y; Y=Cl, OC6H13, Ar') were cleaved under standard conditions by alkali metal amalgams (M/Hg; M=Li, Na, K) to the corresponding sulfinate salts (ArSO2M) and MY, as shown in Eq. 1.The substrates ArSO2Y in toluene were not cleaved by Li/Hg alone; first on addition of an equimolar amount of i-propanol could conversions of almost 100percent be achieved. (Tables I,II,III).A series of six n-hexylarylsulfonates were studied under standard conditions, to establish the influence of the reaction medium and the amalgam on the course of reaction, (Table II).The sterically hindered arylsulfonates ArSO2OC6H13, (Ar= mesityl, 2,4,6-tri-isopropyl) were "anomalous", i.e. underwent fission at the ring/sulfur bond , as shown by Eq. 2.Table III describes the reductive fission of mesityl-phenylsulfone and dimesitylsulfone.
- Horner, Leopold,Schmitt, Rolf-Erhard
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p. 301 - 308
(2007/10/02)
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- FACILE REDUCTION OF SULFINIC ACID TO DISULFIDE WITH THIOL AND CHLOROTRIMETHYLSILANE
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Sulfinic acids were found to be readily reduced to the corresponding disulfide quantitatively at room temperature upon treatment with a mixture of thiols and chlorotrimethylsilane.
- Oae, Shigeru,Togo, Hideo,Numata, Tatsuo,Fujimori, Ken
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p. 1193 - 1196
(2007/10/02)
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