- Reactions of nitrosalicylic aldehydes with chloromethyl tolyl sulfone anion. Synthesis of 2-hydroxydihydrobenzofurans
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Vicarious nucleophilic substitution of hydrogen (VNS) with chloromethyl tolyl sulfone carbanion does not occur in 3-, 4- and 5-nitrosalicylaldehydes. Instead, nucleophilic addition to the carbonyl group takes place leading to 2-hydroxydihydrobenzofurans.
- Makosza, Mieczyslaw,Ziobrowski, Tadeusz,Kwast, Andrzej
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Read Online
- Copper-catalyzed aerobic oxidative cross-coupling reactions of vinylarenes with sulfinate salts: A direct approach to β-ketosulfones
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A copper-catalyzed aerobic oxidative cross-coupling reactions for the synthesis of β-ketosulfones via formation of a C[sbnd]S bond has been demonstrated. Promoted by the crucial copper catalyst, perfect selectivity and good to excellent yields could be achieved. This method, including inexpensive copper catalyst, wide functional group tolerance, and open air conditions, make it very attractive and practical. More importantly, it also provides a versatile tool for the construction of β-ketosulfones from basic starting materials under mild conditions.
- Chen, Yu,Xu, Lei,Wang, Biyu,Jiang, Jingjing,Sun, Yixiang,Li, Longchun
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- Method for synthesizing beta-ketosulfone derivative under mild condition and obtained beta-ketosulfone derivative
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The invention discloses a method for synthesizing a beta-ketosulfone derivative under a mild condition, which comprises the following steps: dissolving aryl olefin and sodium sulfinate in a solvent in a reaction container, adding an acidic additive, sealing the reaction container under the conditions that air exists in the reaction container and no transition metal exists, and purifying after reaction to obtain the beta-ketosulfone derivative. The free radical addition oxidation reaction of olefin and sulfinic acid can be realized under the mild condition without transition metal, the reaction raw materials are cheap and easy to obtain, no organic metal reagent or transition metal is needed, air is used as an oxidizing agent, no dangerous peroxide or persulfide is needed, and the method is compatible with air. The method has the advantages of simple operation and the like, and overcomes the defects of transition metal participation, large catalyst consumption, expensive reagents, high method cost, more reaction steps, more by-products and the like in the prior art.
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Paragraph 0050; 0051
(2021/08/28)
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- Dioxygen-Triggered Oxosulfonylation/Sulfonylation of Terminal Olefins toward β-Keto Sulfones/Sulfones
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A dioxygen-triggered oxosulfonylation/sulfonylation of unactivated olefins to achieve β-keto sulfones/sulfones has been developed. Interestingly, pluralistic mechanisms were found when different types of compounds were applied as substrates, and different products were achieved. The reaction is carried out with a high atomic efficiency in the absence of a metal and a catalyst at room temperature under an air atmosphere. Importantly, as a proof-of-concept, a bioactive molecule was synthesized on a gram-scale level using this method.
- Wang, Yanjie,Zhao, Yuhan,Cai, Changqun,Wang, Lingyun,Gong, Hang
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supporting information
p. 8296 - 8301
(2021/11/13)
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- Photosensitizer-free synthesis of β-keto sulfones: Via visible-light-induced oxysulfonylation of alkenes with sulfonic acids
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A practical and environment-friendly methodology for the construction of β-keto sulfones through visible-light induced direct oxysulfonylation of alkenes with sulfonic acids at ambient temperature under open-air conditions was developed. Most importantly, the reaction proceeded smoothly without the addition of any photocatalyst or strong oxidant, ultimately minimizing the production of chemical waste.
- Hong, Yun-Yun,Peng, Sha,Peng, Zhen,Tang, Shan-Shan,Xie, Long-Yong,Xu, Xiang-Qun,Yang, Li-Hua
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supporting information
p. 4537 - 4541
(2021/05/31)
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- Facile One-Pot Access to α-Diazo-β-ketosulfones from Sulfonyl Chlorides and α-Haloketones
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A convenient one-pot approach to the preparation of α-diazo-β-ketosulfones from sulfonyl chlorides is described. It involves the conversion of the sulfonyl chloride to sodium sulfinate, alkylation of the latter with α-haloketones followed by diazo transfer using the 'sulfonyl-azide-free' ('SAFE') protocol in aqueous medium. The simple and expedient method relies on readily available starting materials and provides facile access to a wide variety of valuable diazo reagents for organic synthesis.
- Dar'In, Dmitry,Kantin, Grigory,Bakulina, Olga,Krasavin, Mikhail
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p. 2259 - 2266
(2020/08/26)
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- Method for synthesizing beta-carbonyl sulfone compound
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The invention discloses a method for synthesizing a beta-carbonyl sulfone compound. The method comprises the steps that sulfinate and a carbonyl compound containing alpha-position active hydrogen areused as raw materials, in a solvent, under the oxidation of alkali, sodium iodide, nanomicelle and 1,2-dibromoethane, the reaction is carried out at 60-80 DEG C for 10-12 hours, separation and purification are performed, and the beta-carbonyl sulfone compound is obtained. The method is simple in synthesis process, convenient in operation, mild in reaction condition, low in cost and high in yield,does not use transition metal catalysis, and is green and safe.
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Paragraph 0024; 0025
(2019/06/13)
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- Heterogeneous copper-catalyzed oxidative coupling of oxime acetates with sodium sulfinates: An efficient and practical synthesis of β-keto sulfones
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An efficient and practical route to β-keto sulfones has been developed through heterogeneous oxidative coupling of oxime acetates with sodium sulfinates by using an MCM-41-supported Schiff base-pyridine bidentate copper (II) complex [MCM-41-Sb,Py-Cu (OAc)2] as the catalyst and oxime acetates as an internal oxidant, followed by hydrolysis. The reaction generates a variety of β-keto sulfones in good to excellent yields. This new heterogeneous copper (II) catalyst can be easily prepared via a simple procedure from readily available and inexpensive reagents and exhibits the same catalytic activity as Cu (OAc)2. MCM-41-Sb,Py-Cu (OAc)2 is also easy to recover and is recyclable up to eight times with almost consistent activity.
- Xia, Jianhui,Huang, Xue,You, Shengyong,Cai, Mingzhong
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- Efficient sulfonylation of ketones with sodium sulfinates for the synthesis of β-keto sulfones
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The oxidative sulfonylation of ketones with sodium sulfinates as the sulfone source and DMSO as the oxidant is reported. A series of β-keto sulfones were obtained in good to excellent yields. The advantages of this efficient protocol include the low cost of DMSO and HBr, and a broad scope.
- Deng, Siqi,Liang, En,Wu, Yinrong,Tang, Xiaodong
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p. 3955 - 3957
(2018/09/27)
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- Dual-tail arylsulfone-based benzenesulfonamides differently match the hydrophobic and hydrophilic halves of human carbonic anhydrases active sites: Selective inhibitors for the tumor-associated hCA IX isoform
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The synthesis and characterization of two new sets of arylsulfonehydrazone benzenesulfonamides (4a-4i with phenyl tail and 4j-4q with tolyl tail) are reported. The compounds were designed according to a dual-tails approach to modulate the interactions of the ligands portions at the outer rim of both hydrophobic and hydrophilic active site halves of human isoforms of carbonic anhydrase (CA, EC 4.2.1.1). The synthesized sulfonamides were evaluated in vitro for their inhibitory activity against the following human (h) isoforms, hCA I, II, IV and IX. With the latter being a validated anticancer drug target and a marker of tumor hypoxia, attractive results arose from the Compounds’ inhibitory screening in terms of potency and selectivity. Indeed, whereas the first subset of compounds 4a-4i exhibited great efficacy in inhibiting both the ubiquitous, off-target hCA II (KIs 9.5–172.0 nM) and hCA IX (KIs 7.5–131.5 nM), the second subset of tolyl-bearing derivatives 4j-4q were shown to possess a selective hCA IX inhibitory action over isoforms I, II and IV. The most selective compounds 4l and 4n were further screened for their in vitro cytotoxic activity against MCF-7 and MDA-MB-231 cancer cell lines under hypoxic conditions. The selective IX/II inhibitory trend of 4j-4q compared to those of compounds 4a-4i was unveiled by docking studies. Further exploration of these molecules could be useful for the development of novel antitumor agents with a selective CA inhibitory mechanism.
- Ibrahim, Hany S.,Allam, Heba Abdelrasheed,Mahmoud, Walaa R.,Bonardi, Alessandro,Nocentini, Alessio,Gratteri, Paola,Ibrahim, Eslam S.,Abdel-Aziz, Hatem A.,Supuran, Claudiu T.
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- Regiocontrolled synthesis of α-sulfonylmethyl o-nitrostyrenes via ZnI2-mediated sulfonylation and AgNO2/Pd(PPh3)4-promoted o-nitration
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We report herein the AgNO2/Pd(PPh3)4-promoted regiocontrolled o-nitration of α-sulfonylmethylstyrenes in MeNO2 with good yields. The o-nitration process provides a series of sulfonyl o-nitrostyrenes. Substituted α-sulfonylmethylstyrenes were synthesized from ZnI2-mediated sulfonylation of substituted α-methylstyrenes and sodium sulfinates (RSO2Na) in MeCN with good to excellent yields. The structures of the key products were confirmed by X-ray crystallography. A plausible mechanism has been proposed herein.
- Chang, Meng-Yang,Chen, Han-Yu,Wang, Heui-Sin
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p. 10601 - 10610
(2018/05/31)
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- Synthesis and antifungal activity of novel oxazolidin-2-one-linked 1,2,3-triazole derivatives
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Novel oxazolidin-2-one-linked 1,2,3-triazole derivatives (4a-k) were synthesized by straightforward and versatile azide-enolate (3 + 2) cycloaddition. The series of compounds was screened for antifungal activity against four filamentous fungi as well as six yeast species of Candida spp. According to their efficiency and breadth of scope, they can be ordered as 4k > 4d > 4h > 4a, especially in relation to the activity displayed against Candida glabrata ATCC-34138, Trichosporon cutaneum ATCC-28592 and Mucor hiemalis ATCC-8690, i.e. compounds 4d, 4h and 4k showed excellent activity against C. glabrata (MIC 0.12, 0.25 and 0.12 μg mL-1, respectively), better than that of itraconazole (MIC 1 μg ml-1). The activity of compound 4d (MIC = 2 μg mL-1) was higher than that observed for the standard antifungal drug (MIC = 8 μg mL-1) against Trichosporon cutaneum, while compound 4k displayed an excellent antimycotic activity against Mucor hiemalis (MIC = 2 μg mL-1vs. 4 μg mL-1 for itraconazole). In addition, we describe herein a novel mild and eco-friendly synthetic protocol for obtaining β-ketosulfones (adducts to afford compounds 4a-k) from α-brominated carbonyls in an aqueous nanomicellar medium at room temperature.
- Ramírez-Villalva, Alejandra,González-Calderón, Davir,Rojas-García, Roxana I.,González-Romero, Carlos,Tamaríz-Mascarúa, Joaquín,Morales-Rodríguez, Macario,Zavala-Segovia, Nieves,Fuentes-Benítes, Aydeé
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supporting information
p. 2258 - 2262
(2017/12/26)
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- Metal-free and selective cleavage of unstrained carbon–carbon single bonds: Synthesis of β-ketosulfones from β-chlorohydrins and sodium sulfinates
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A metal-free protocol for the selective cleavage of unstrained C–C single bonds was developed. Under the catalysis of KI and in the presence of NaHCO3, the readily available α-chloro-β-hydroxy ketones underwent bond breaking and sulfonylation smoothly to afford β-ketosulfones with high efficiency and broad substrate scope. Mechanism investigations, both experimental and theoretical, showed that a retro-aldol cleavage/nucleophilic substitution sequence might be involved.
- Li, Yanni,Liang, Deqiang,Chang, Yu,Li, Xiangguang,Fu, Shaoguang,Yuan, Yunli,Wang, Baoling
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supporting information
p. 2044 - 2052
(2017/10/23)
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- Method for efficiently synthesizing beta-ketone sulfonyl compounds through visible light induction
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The invention provides a method for efficiently synthesizing beta-ketone sulfonyl compounds through visible light induction. The method specifically comprises steps as follows: in the presence of an organic solvent and at the room temperature, enol sulfonate compounds are taken as a raw material and react for 1-12 h through induction of visible light under the catalysis action of an organic compound serving as a photocatalyst, and the beta-ketone sulfonyl compounds are prepared. Compared with an existing method, the method has a wide applicable substrate range, a substrate is convenient and easy to obtain, reaction conditions are mild, operation is simple and convenient, the reaction efficiency is high, and the method has huge value in industrial application.
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Page/Page column 7
(2017/07/21)
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- Copper Triflate Mediated α-Monohalogenation of α-Diazo β-Ketosulfones with Ammonium Halides
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Copper triflate mediated α-monohalogenation of α-diazo β-ketosulfones with ammonium halides provides the corresponding α-halo β-ketosulfones. Different metal triflates are investigated for this facile and efficient transformation. A plausible mechanism is proposed.
- Chan, Chieh-Kai,Wang, Heui-Sin,Hsu, Ru-Ting,Chang, Meng-Yang
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p. 2045 - 2056
(2017/04/26)
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- Construction of Sulfonyl Oxabenzo[3.3.1]bicyclic Core via Cyclocondensation of β-Ketosulfones and o-Formyl Allylbenzenes
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NH4OAc mediated domino Knoevenagel/Diels-Alder cyclocondensation of β-ketosulfones 1 and o-formyl allylbenzenes 2 provides sulfonyl oxabenzo[3.3.1]bicyclic core 4 in a cosolvent of toluene and HOAc (v/v = 1/1) at reflux for 3 h. The intermediate 3 contains a chalcone motif. The uses of various ammonium salts and solvent systems are investigated for facile and efficient transformation. The plausible mechanisms have been proposed and the DFT calculations have been included.
- Hsueh, Nai-Chen,Chen, Hsing-Yin,Chang, Meng-Yang
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p. 13324 - 13332
(2017/12/26)
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- Visible-light initiated direct oxysulfonylation of alkenes with sulfinic acids leading to β-ketosulfones
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Visible light along with 1 mol% eosin Y catalyzed the direct oxysulfonylation of alkenes with sulfinic acids via a photoredox process which has been developed at room temperature under transition-metal-free conditions. The present reaction provides a highly efficient approach to diverse β-ketosulfones in moderate to good yields. It should provide a promising synthesis candidate for the formation of diverse and useful β-ketosulfone derivatives in the fields of synthetic and pharmaceutical chemistry.
- Yang, Daoshan,Huang, Ben,Wei, Wei,Li, Jin,Lin, Gu,Liu, Yaru,Ding, Jiehua,Sun, Pengfei,Wang, Hua
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supporting information
p. 5630 - 5634
(2016/10/22)
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- Tetrabutylammonium iodide-catalyzed oxidative coupling of enamides with sulfonylhydrazides: Synthesis of β-keto-sulfones
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A facile synthetic route towards pharmaceutically interesting β-keto-sulfone derivatives by tetrabutylammonium iodide (TBAI)/tert-butyl hydroperoxide (TBHP) mediated oxidative coupling of readily prepared enamides with economical sulfonylhydrazides is described. The corresponding β-keto-sulfone compounds were obtained in moderate to good yields. The present method is metal-free and base-free and shows tolerance to a variety of functional groups. This journal is
- Tang, Yucai,Zhang, Ye,Wang, Kaifeng,Li, Xiaoqing,Xu, Xiangsheng,Du, Xiaohua
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p. 7084 - 7090
(2015/06/30)
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- Synthesis, in vitro and in Silico studies of some novel 5-nitrofuran-2-yl hydrazones as antimicrobial and antitubercular agents
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In this study, we synthesized two series of novel 5-nitrofuran-2-carbohydrazides 21a-h and 22a-e in addition to a third series of thiophene-2-carbohydrazides 23a-g to develop potent antimicrobial and/or antitubercular agents. The newly synthesized compounds were evaluated in vitro for their antimicrobial and antimycobacterial activities. Most of the 5-nitrofuran-2-carbohydrazides 21a-h and 22a-e displayed variable activity against Aspergillus fumigates, Staphylococcus aureus, Streptococcus pneumonia, Bacillis subtilis, Salmonella typhimurium, Klebsiella pneumonia, Escherichia coli and Mycobacterium tuberculosis. The sulfonamide derivative 21f exhibited superior potency and broad-spectrum antimicrobial activity with minimum inhibitory concentration (MIC)=0.06-0.98 μg/mL and antimycobacterial activity with MIC=3.9 μg/mL. The 5-nitrofuran-2-carbohydrazides 21a, b, g, h and 22a-c exhibited significant antibacterial activity with MIC values in the range of 0.12-7.81 μg/mL. The significances of the 5-nitrofuran moiety and sulfonamide function were explored via the structure-activity relationship (SAR) study. In addition, docking studies revealed that the p-amino benzoic acid (PABA) and binding pockets of the dihydropteroate synthase (DHPS) were successfully occupied by compound 21f. Furthermore, two quantitative structure-activity relationship (QSAR) models were built to explore the structural requirements which controlled the activity.
- Abdel-Aziz, Hatem Abdel-Kader,Eldehna, Wagdy Mohamed,Fares, Mohamed,Elsaman, Tilal,Abdel-Aziz, Marwa Mostafa,Soliman, Dalia Hussein
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p. 1617 - 1630
(2015/11/24)
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- Copper-catalyzed coupling of oxime acetates with sodium sulfinates: An efficient synthesis of sulfone derivatives
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Sulfone derivatives are important synthetic intermediates. However, the general method for their preparation is through traditional coupling reaction: the alkylation of sodium sulfinates with phenacyl halides. Based on our previous work on sodium sulfinates and oxime acetates, we herein report a novel method for sulfone derivatives by oxidative coupling with sodium sulfinates and oxime acetates using copper as catalyst. The sulfonylvinylamine products could be formed in excellent yields. Upon hydrolysis by silica gel in CH 2Cl2, β-ketosulfones could also be efficiently constructed. Various sulfonylvinylamines and β-ketosulfones were obtained in good to excellent yields under the optimized reaction conditions. Mechanistic studies indicated that this transformation involved copper-catalyzed N-O bond cleavage, activation of a vinyl sp2 C-H bond, and C-S bond formation. The oxime acetates act as both a substrate and an oxidant, thus the reaction needs no additional oxidants or additives. Copper brings us together: The title reaction involves copper-catalyzed N-O bond cleavage, activation of a vinyl sp2 C-H bond and C-S bond formation; it uses simple oxime acetates and sodium sulfinates to synthesize sulfonylvinylamine products without the need for additional oxidants or additives. Upon hydrolysis, useful β-ketosulfones are obtained.
- Tang, Xiaodong,Huang, Liangbin,Xu, Yanli,Yang, Jidan,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 4205 - 4208
(2014/05/06)
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- Synthesis of ionic liquid-supported hypervalent iodine reagent and its application as a 'catch and release' reagent for α-substituted acetophenones
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A novel imidazolium-based ionic liquid-supported hypervalent iodine reagent has been synthesized and employed for a 'catch and release' strategy with substituted acetophenones to generate various α-substituted acetophenones in good to excellent yields. The use of an ionic liquid-supported hypervalent iodine reagent avoids chromatographic separation for the purification of α-substituted acetophenones and thus makes the method greener.
- Muthyala, Manoj Kumar,Choudhary, Sunita,Kumar, Anil
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p. 14297 - 14303
(2014/04/17)
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- Synthesis of 2-arylbenzimidazole analogues
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Substituted 2-arylbenzimidazoles (4) were easily synthesized in good yields starting from the condensation reaction of 1,2-diaminobenzenes (1) with β-ketosulfones (5) in the presence of boiling HOAc.
- Chang, Meng-Yang,Chan, Chieh-Kai,Chen, Yi-Chia
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p. 1229 - 1236
(2014/05/20)
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- Sulfonation and trifluoromethylation of enol acetates with sulfonyl chlorides using visible-light photoredox catalysis
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A mild, practical method to prepare α-sulfonyl and α-trifluoromethyl ketones from readily available enol acetates and sulfonyl chlorides has been developed using visible-light photoredox catalysis. The method could be used with a wide range of enol acetates and sulfonyl chlorides, and gave the desired products in satisfactory to excellent yields. A practical method to prepare α-sulfonyl and α-trifluoromethyl ketones from enol acetates and sulfonyl chlorides using visible-light photoredox catalysis is presented. Copyright
- Jiang, Heng,Cheng, Yuanzheng,Zhang, Yan,Yu, Shouyun
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supporting information
p. 5485 - 5492
(2013/09/02)
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- Microwave-assisted manganese(III) acetate based oxidative cyclizations of alkenes with β-ketosulfones
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The microwave-assisted synthesis of 5-(4-nitrophenyl)-2-phenyl-4-(phenylsulfonyl)-2,3-dihydrofuran (5a) was performed via manganese(III) acetate based oxidative cyclization of 1-(4-nitrophenyl)-2-(phenylsulfonyl)ethanone (3a) with vinylbenzene (4a). This
- Curti, Christophe,Crozet, Maxime D.,Vanelle, Patrice
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experimental part
p. 200 - 205
(2009/04/07)
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- Rapid synthesis of sulfone derivatives as potential anti-infectious agents
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An original one-pot microwave reaction was developed for the synthesis of sulfone derivatives as new potent antimicrobial agents. This eco-friendly methodology conducted in 30 min led to desired products with good yields. The sulfones (4a and 4b) were obtained via the reaction of 3a with the corresponding halo-derivatives in the presence of sodium hydride. All compounds were tested for their antibacterial and antifungal activities against four bacterial strains (two gram positive, and two gram negative ones) and two yeasts. The disk diffusion method has shown an interesting antibacterial activity for seven compounds (3b-g and 4b) against Staphylococcus aureus. Among these seven compounds, five derivatives (3b-e and 3g) showed activity against Candida tropicalis.
- Curti,Laget,Carle, A. Ortiz,Gellis,Vanelle
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p. 880 - 884
(2008/02/12)
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- Reactions of sulfonyl chlorides with silyl enol ethers catalysed by a ruthenium(II) phosphine complex: Convenient synthesis of β-keto sulfones
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The reactions of alkane- and arene-sulfonyl chlorides with silyl enol ethers in the presence of a ruthenium(II) phosphine complex are found to give β-keto sulfones in good to high yields.
- Kamigata, Nobumasa,Udodaira, Kumiko,Shimizu, Toshio
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p. 783 - 786
(2007/10/03)
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