- Acridine Orange Hemi(Zinc Chloride) Salt as a Lewis Acid-Photoredox Hybrid Catalyst for the Generation of α-Carbonyl Radicals
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A readily accessible organic-inorganic hybrid catalyst is reported for the reductive fragmentation of α-halocarbonyl compounds. The robust hybrid catalyst is a self-stabilizing combination of ZnCl2 Lewis acid and acridine orange as the photoactive organic dye. Mechanistic specifics of this hybrid catalyst have been studied in detail using both photophysical and electrochemical experiments. A systematic study enabled the discovery of the appropriate Lewis acid for the effective LUMO stabilization of α-halocarbonyl compounds and thereby lowering of reduction potential within the range of a standard organic dye. This strategy resolves the issues like dehalogenative hydrogenation or homo-coupling of alkyl radicals by guiding the photoredox cycle through an oxidative quenching pathway. The cooperativity between the photoactive organic dye and the Lewis acid counterparts empowers functionalization with a wide range of coupling partners through efficient and controlled generation of alkyl radicals and serves as an appropriate alternative to the expensive late transition metal-based photocatalysts. To demonstrate the application potential of this cooperative catalytic system, four different synthetic transformations of α-carbonyl bromides were explored with broad substrate scopes.
- Das, Sanju,De Sarkar, Suman,Mandal, Tanumoy
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supporting information
(2021/12/10)
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- Cu(OTf)2-Catalyzed efficient sulfonylation of vinyl azides with sodium sulfinates
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A simple oxidative cross-coupling reaction between vinyl azides and sodium sulfinates was developed. This reaction uses commercial arylsulfinates that are more efficient, cheaper, and more stable as sulfonylation reagents, for efficiently, cheaply, and environmentally friendly synthesis of β-keto sulfones. And the reaction has the advantages of simple operation, high efficiency, good yield, and also has a wide range of functional group tolerance.
- Ning, Zhitao,Xu, Zheng,Liu, Ruikai,Du, Zhengyin
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supporting information
p. 3492 - 3500
(2021/10/14)
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- Copper-Catalyzed Aerobic Oxidative Cleavage of Unstrained Carbon-Carbon Bonds of 1,1-Disubstituted Alkenes with Sulfonyl Hydrazides
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Alkoxy radical-mediated carbon-carbon bond cleavages have emerged as a powerful strategy to complement traditional ionic-type transformations. However, carbon-carbon cleavage reaction triggered by alkoxy radical intermediate derived from the combination of alkyl radical and dioxygen, is scarce and underdeveloped. Herein, we report alkoxy radical, which was generated from alkyl radical and dioxygen, mediated selective cleavage of unstrained carbon-carbon bond for the oxysulfonylation of 1,1-disubstituted alkenes, providing facile access to a variety of valuable β-keto sulfones. Mechanistic experiments indicated alkoxy radical intermediate that underwent subsequent regioselective β-scission might be involved in the reaction and preliminary computational studies were conducted to provide a detailed explanation on the regioselectivity of the C—C bond cleavage. Notably, the strategy was successfully applied for constructing uneasily obtained architecturally intriguing molecules.
- Yi, Dong,He, Linying,Qi, Zhongyu,Zhang, Zhijie,Li, Mengshun,Lu, Ji,Wei, Jun,Du, Xi,Fu, Qiang,Wei, Siping
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supporting information
p. 859 - 865
(2021/03/04)
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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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- Oxy-sulfonylation of terminal alkynesviaC-S coupling enabled by copper photoredox catalysis
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We report the first literature example using visible light-induced trimethylsilyl azide (TMS-N3)-assisted copper-catalyzed oxy-sulfonylation of terminal C-C bonds to form β-keto sulfones (C-S bond formation). TMS-N3promotes the reaction by facilitating the formation of sulfonyl radicals, which later decompose into N2gas upon light irradiation. This method involves the use of commercially available and stable starting materials. Also, a wide range of functional groups have been well-tolerated under the current photoredox process, evading the side product formation. Potent biologically active compounds, such as CES1, 11β-HSD1 inhibitors, anti-analgesic agents, and reactive synthesis intermediates were synthesized to demonstrate the synthetic utility of the current methodology. Moreover, green chemistry metrics and Eco-scale evaluation for the current photochemical method show that the protocol is eco-friendly and highly efficient.
- Charpe, Vaibhav Pramod,Das, Deb Kumar,Hwang, Kuo Chu,Hwu, Jih Ru,Lin, Chun-Cheng,Pampana, V. K. K.,Sagadevan, Arunachalam
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supporting information
p. 3569 - 3574
(2021/06/06)
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- Sulfated tungstate/dioxygen: A new catalytic system for oxysulfonylation of styrenes to form β-keto sulfones
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A new system for synthesis of a wide range of β-keto sulfones using sulfated tungstate as a heterogeneous catalyst and oxygen as an environmentally benign oxidant with aryl hydrazides and styrenes as reacting counterparts has been developed. The preliminary experimental results support the involvement of free radical species. Thus, aryl sulfonyl free radicals, generated by oxidation of aryl sulfonyl hydrazides, subsequently undergo a tandem addition to styrenes to form intermediate benzyl free radicals, and oxygen capture and oxidation to furnish β-keto sulfones. The method is mild and efficient with easy workup procedures. The catalyst is recyclable. This journal is
- Akamanchi, Krishnacharya G.,Autade, Snehalata B.,Kulkarni, Raghavendra V.,Wagh, Ganesh D.
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p. 10554 - 10561
(2020/07/14)
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- Electrochemical Synthesis of β-Ketosulfones from Switchable Starting Materials
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A synthesis of β-ketosulfones via sulfination of aryl methyl ketones and aryl acetylenes with sodium sulfinates under mild electrochemical conditions, in moderate to good chemical yields, is described. In particular, an electrochemical sulfination reaction of alkynes with sulfinate salts has never been explored. An environmentally friendly characteristic of this reaction is that it uses electricity as a valuable energy source for electrochemical synthesis of β-ketosulfones. This strategy is more convenient and practical compared to previous approaches.
- Yavari, Issa,Shaabanzadeh, Sina
-
supporting information
p. 464 - 467
(2020/01/31)
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- Preparation method of beta-carbonyl sulfone compound
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The invention discloses a preparation method of a beta-carbonyl sulfone compound, and belongs to the technical field of organic synthesis. The preparation method of the beta-carbonyl sulfone compoundis provided for solving the problems that in the prior art, operation is complex, the substrate range is narrow, and the functional group tolerance is poor. The preparation method comprises the stepsof taking a compound shown in formula I and a compound shown in formula II as raw materials, taking copper salt as a catalyst, carrying out reaction in an organic solvent, and after the reaction is completed, carrying out aftertreatment to obtain the beta-carbonyl sulfone compound. The preparation method is simple and convenient to operate, mild in reaction condition, wide in substrate range and good in functional group tolerance, the yield reaches up to 93%, and the synthesis cost is remarkably reduced.
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Paragraph 0039-0042; 0059-0062
(2020/12/09)
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- Visible light promoted sulfonylation and sulfonylcarbonylation of alkenes
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Visible light promoted sulfonylation and sulfonylcarbonylation reactions of readily available alkenes with TosMIC for the synthesis of valuable vinyl sulfones and β-keto sulfones were described. A reasonable radical involved mechanism is proposed.
- Min, Wenjian,Guo, Guozhe,Yang, Caixia,Huo, Congde
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supporting information
(2020/05/26)
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- A Naphthalimide-Based ND-O-EAc Photocatalyst for Sulfonation of Alkenes to Access β-Ketosulfones Under Visible Light
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The development of facile, efficient, cost-effective, and visible light-driven photocatalysts for organic synthetic chemistry has received increasing attention. This protocol has initially synthesized a naphthalimide-based ND-O-EAc visible light photocatalyst for the sulfonation of alkenes to produce β-ketosulfones. Compared with the current photosynthetic strategies, the newly developed catalytic system has some merits, namely high efficiency, gram-scale preparation of low-cost photocatalyst, no metal contamination, wide substrate scope, and green terminal oxidant of air. Moreover, the prepared photocatalyst of ND-O-EAc is feasible for the sulfonation reactions of androstenones. Importantly, such a photocatalysis strategy can easily realize the scale-up synthesis for β-ketosulfone drugs under the mild conditions up to 90 % yield.
- Yang, Xiaoting,Yang, Jianjing,Yan, Kelu,Qin, Hongyun,Dong, Wenjie,Wen, Jiangwei,Wang, Hua
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supporting information
p. 3456 - 3461
(2020/06/08)
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- Biomimetic photocatalytic sulfonation of alkenes to access β-ketosulfones with single-atom iron site
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Biomimetic photocatalysis as an important organic transformation strategy has received increasing attention, with the performances of biomimetic catalysts largely depending on their design. This protocol has been initially used to fabricate a biomimetic photocatalyst of single-atom iron site through coupling carbon nitride with hemin (CNH) for the visible light-promoted sulfonation of alkenes to produce β-ketosulfones with up to 94% yield. The experimental results show that the role of CN in CNH is concentrated on enhancing the separation ability of photogenerated electron pairs and holes to improve the photocatalytic activity and stability. Moreover, the as-prepared photocatalyst of single atom iron can be irradiated under near-infrared light with a satisfactory yield, and is also feasible for the sulfonation reactions of androstenones. Importantly, this biomimetic catalysis-based synthesis system has some merits, namely high catalysis efficiency, favorable recyclability, high turnover number, and excellent functional group tolerance, making it promising for extensive applications in organic transformations for the synthesis of β-ketosulfones to access various bioactive drugs.
- Wen, Jiangwei,Yang, Xiaoting,Sun, Zongzhao,Yang, Jianjing,Han, Ping,Liu, Qiuxia,Dong, Hongyan,Gu, Meng,Huang, Limin,Wang, Hua
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supporting information
p. 230 - 237
(2020/01/21)
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- Metal-Free Electrochemical Coupling of Vinyl Azides: Synthesis of Phenanthridines and β-Ketosulfones
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We reported an efficient and environmentally benign electrochemical synthesis of phenanthridines by oxidative coupling of vinyl azides with sodium azide or benzenesulfonyl hydrazides, for the first time. The reaction conditions are mild, and no additional metal-catalyst or exogenous oxidants are needed. The protocol has broad substrate scope and high functional group tolerance. Furthermore, this green electrochemical procedure can be readily extended to the synthesis of β-ketosulfones. Gram scale reactions further demonstrate the practicability.
- Chen, Qianjin,Kong, Xianqiang,Li, Guodong,Liang, Qi,Lin, Long,Xu, Bo,Yu, Ke
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p. 6135 - 6145
(2020/10/06)
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- Visible-light promoted aerobic difunctionalization of alkenes with sulfonyl hydrazides for the synthesis of β-keto/hydroxyl sulfones
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A practical method has been developed for the conversion of alkenes to β-keto/hydroxyl sulfones by their reaction with sulfonyl hydrazides under metal-free conditions. This reaction proceeds through the oxidative addition of alkenes by sulfonyl radicals that are generated by visible-light induced oxidation of sulfonyl hydrazides. Notaly the reaction uses O2 as the terminal oxidant, instead of metal catalysts or oxidants like TBHP, leading to H2O and N2 as the clean by-products. The key features of this reaction include readily available reagents, mild reaction conditions and broad substrate scope.
- Wu, Jie,Zhang, Yulan,Gong, Xinchi,Meng, Yunge,Zhu, Chunyin
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supporting information
p. 3507 - 3513
(2019/04/14)
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- Beta-keto sulfone derivatives as well as preparation method and application thereof
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The invention discloses beta-keto sulfone derivatives as well as a preparation method and application thereof. The preparation method includes the following step: performing a reaction by using olefinazide and sulfonyl hydrazide as starting material, CuSO.5HO as a catalyst and water as a reaction solvent at 90 DEG C for 2-4 h. According to the method provided by the invention, the catalystCuSO.5HO is used in the reaction system, so that the reaction is effectively promoted, a self-coupling reaction of the sulfonyl hydrazide is inhibited, and the yield of the reaction is improved;meanwhile, the reaction reagents and catalyst used in the method are stable, cheap and easy to obtain, mass production is facilitated, and a novel effective way is provided for construction of the structures; the reaction solvent is water, and has the advantages of green economy and environmental protection; and in addition, results of activity experiments show that the product can inhibit 11 beta-hydroxysteroid dehydrogenase to a certain extent, so that the preparation method and the product have important application significance in the field of medicine.
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Paragraph 0041; 0042; 0055-0058
(2020/01/03)
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- Method for preparing beta-keto sulfone or beta-hydroxy sulfone from reaction of substituted olefin and sulfonyl hydrazine derivative
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The invention belongs to the technical field of organic chemical synthesis and specifically relates to a method for preparing beta-keto sulfone or beta-hydroxy sulfone from reaction of substituted olefin and sulfonyl hydrazine derivative. The method comprises the following steps: taking substituted olefin and sulfonyl hydrazine derivative as raw materials, taking air as an oxidizing agent and performing oxidizing addition reaction under the existence of photosensitizer and alkali and under the condition of visible light irradiation, thereby generating beta-keto sulfone or beta-hydroxy sulfone.The method provided by the invention is low in cost of raw materials, simple in process, green and safe, efficient and environment-friendly, and suitable for industrial production.
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Paragraph 0017; 0018; 0019; 0020
(2019/02/06)
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- Preparation method of oxalyl sulfonyl hydrazide and application of oxalyl sulfonyl hydrazide in olefin sulfonation reaction
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The invention belongs to the technical field of organic chemical synthesis and particularly relates to a preparation method of oxalyl sulfonyl hydrazide and application of the oxalyl sulfonyl hydrazide in olefin sulfonation reaction. The preparation metho
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-
Paragraph 0025; 0026-0027
(2019/05/28)
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- NBS-mediated synthesis of β-keto sulfones from benzyl alcohols and sodium arenesulfinates
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An efficient synthetic route towards the synthesis of β-keto sulfones has been developed from secondary benzyl alcohols using N-bromosuccinimide (NBS). The present protocol utilizes NBS as oxidant as well as brominating agent, readily accessible benzyl alcohols and sodium arenesulfinates as the sulfonylating reagent under mild conditions. The control experiments revealed that the reaction proceeds via oxidation of alcohol to ketone, α-bromination of ketone and nucleophilic substitution by sodium arenesulfinate. Furthermore, the efficiency of the methodology was tested with a gram scale reaction and also shown the synthetic utility.
- Muneeswara, Madithedu,Sundaravelu, Nallappan,Sekar, Govindasamy
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supporting information
p. 3479 - 3484
(2019/05/21)
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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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- One-pot synthesis of chiral β-hydroxysulfones from alkynes: Via aerobic oxysulfonylation and asymmetric reduction in MeOH/H2O
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A highly enantioselective synthesis of β-hydroxysulfones from inexpensive and readily available terminal alkynes and sodium sulfinates via a consecutive one-pot reaction in an aqueous medium under mild conditions is described. The intermediates, β-keto sulfones, generated from an aerobic oxysulfonylation of terminal alkynes and sodium sulfinates catalyzed by an iron salt in MeOH/H2O (v : v = 3 : 1) at 50 °C, were subsequently reduced by a Ru-catalyzed asymmetric transfer hydrogenation with HCOONa as a hydrogen source. A variety of chiral β-hydroxysulfones were obtained in good yields and up to 99.9% ee values. This one-pot process could be easily scaled up for gram-scale synthesis.
- Cui, Peng,Liu, Qixing,Wang, Juan,Liu, Huan,Zhou, Haifeng
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supporting information
p. 634 - 639
(2019/02/14)
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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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- 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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supporting information
p. 3955 - 3957
(2018/09/27)
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- Metal-free TBAI-catalyzed oxidative Csp3–S bond formation through Csp2–Csp2 bond and S–N bond cleavage: A new route to β-keto-Sulfones
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A novel TBAI-catalyzed radical sulfonylation of readily available N,N-dimethylenaminones with sulfonylhydrazides to afford functionalized β-keto-sulfones has been developed. Various functional groups were tolerated well under the present oxidative conditions and the corresponding β-keto-sulfone compounds were obtained in moderate to good yields. Importantly, this transformation offered the first protocol for Csp3–S bond formation by oxidative Csp2–Csp2 bond cleavage in one step.
- Tang, Yucai,Chen, Ying,Liu, Hui,Guo, Min
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p. 3703 - 3705
(2018/09/14)
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- Synthesizing method of beta-keto sulfone compound
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The invention discloses a synthesizing method of a beta-keto sulfone compound. The synthesizing method includes: mixing a compound I as shown in formula I and a compound II as shown in formula II withan oxidizing agent to obtain mixed liquid, and adding a copper catalyst into the mixed liquid by three times; sequentially subjecting the mixture obtained after the reaction to cation exchange membrane processing and post-processing to obtain the beta-keto sulfone compound as shown in formula III. The synthesizing method has the advantages that the compound I is used as the raw material, the rawmaterial is simple and easy to obtain, the synthesizing route is simple, side reaction is reduced, and high product purity and yield are achieved; the used copper catalyst is cheap and has high specificity to the reaction of the method, the copper catalyst is added by three times and coordinated with the other raw materials, the mixture obtained after the reaction is sequentially subjected to cation exchange membrane processing and post-processing, and the problem that a metal catalyst is hard to separate in the prior art can be well solved.
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Paragraph 0054; 0055; 0057
(2018/09/08)
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- A metal-free and regioselective approach to (Z)-β-fluorovinyl sulfones and their chemoselective hydrogenation to β-fluoroalkyl sulfones
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A highly regioselective, metal-free hydrofluorination reaction of alkynyl sulfones was developed using TBAF—one of the cheapest and most commonly available fluoride sources. In addition, the reactivity of the resulting β-fluorovinyl sulfones was studied, focusing on their selective hydrogenation reaction. Both β-fluorovinyl sulfones and their hydrogenation products β-fluoroalkyl sulfones may find applications in medicinal and agrochemical sciences.
- Sedgwick, Daniel M.,Román, Raquel,Barrio, Pablo,Morales, Cristina,Fustero, Santos
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p. 108 - 116
(2018/01/01)
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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 6
(2017/07/21)
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- Photoinduced rearrangement of vinyl tosylates to β-ketosulfones
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We developed a photoinduced radical fragmentation and rearrangement of vinyl tosylates that enables efficient formation of β-ketosulfones. This process is based on the photoinitiated homolysis of vinyl tosylate to release a sulfinyl radical from the tosyl group and the subsequent addition of a sulfinyl radical to another vinyl tosylate to form the desired β-ketosulfones. This simple protocol features a broad scope with both aromatic and aliphatic substrates, convenient reagents and operating systems.
- Xie, Lili,Zhen, Xiaomeng,Huang, Shuping,Su, Xiaolong,Lin, Mai,Li, Yi
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supporting information
p. 3530 - 3534
(2017/08/15)
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- Preparation method of beta-arone substituted sulfone compounds
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The invention provides a preparation method of beta-arone substituted sulfone compounds. In the method, olefin azide and sulfonyl hydrazide are used as start raw materials; and in an organic solvent, potassium iodide serves as a catalyst while tert-butyl hydroperoxide serves as an oxidizing agent, and the beta-arone substituted sulfone compounds are generated by reactions, wherein the reaction temperature is room temperature, and the reaction time is 2-4 hours. The preparation method provided by the invention has the advantages that the design is reasonable, the raw materials are easily available, no metal catalyst is involved, the reaction conditions are mild, high-temperature backflow is not required, the method is safe and convenient, the yield is high, and the yield of most products is over 70%. The preparation method provided by the invention is an easy-to-operate method for quickly establishing beta-arone substituted sulfone compounds in a mild and diversified manner, wherein the two start raw materials can be obtained by a one-step method, and the reaction raw materials are cheap and easily available. The general formula I of the beta-arone substituted sulfone compounds is shown in the specification.
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Paragraph 0028; 0029; 0030; 0031; 0032; 0037-0040
(2016/10/10)
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- Method for synthesizing aryl sulfone compound as pharmaceutical intermediate
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The invention relates to a method for synthesizing anaryl sulfone compound capably used as a pharmaceutical intermediate and shown by a following formula (III). The method comprises the following steps of reacting a compound represented by a formula (I) with a compound represented by a formula (II) in an organic solvent under the presence of a catalyst, an oxidant, alkali and an accelerant, performing post-treatment after the completion of the reaction so as to obtain a compound represented by the formula (III) in the specification, wherein each of R1 and R2 is independently selected from H, C1-C6 alkyl, C1-C6alkoxy or halogen; X is halogen. The method disclosed by The invention has the advantages that a target product is obtained at a high yield through a novel reaction system composed of the catalyst, the oxidant, the alkali, the accelerant and the organic solvent as well as the selection of appropriate substrates, and the method has excellent application prospects and productive potentialities in organic synthesis, especially in the field of pharmaceutical intermediates.
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Paragraph 0041; 0042; 0043; 0044; 0045
(2016/10/24)
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- Molecular iodine mediated oxidative coupling of enol acetates with sodium sulfinates leading to β-keto sulfones
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An efficient, transition metal-free protocol for direct oxidative sulfonylation of enol acetates with readily available sodium sulfinates has been developed using molecular iodine as an oxidant. The reaction follows a free radical pathway and offers a more practical, economical, safer, and environmentally benign approach to a variety of β-keto sulfones in a one-pot procedure.
- Yadav, Vinod K.,Srivastava, Vishnu P.,Yadav, Lal Dhar S.
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p. 2236 - 2238
(2016/05/10)
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- Iron-Catalyzed Oxidative Sulfonylation of Enol Acetates: An Environmentally Benign Approach to β-Keto Sulfones
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The first application of iron-catalyzed sulfonylation of aryl enol acetates with sulfonyl hydrazides for the construction of β-keto sulfones under aerobic conditions is reported. The present protocol, which utilizes an inexpensive iron salt as the catalyst, readily available sulfonyl hydrazides as the sulfonylating reagents, and air as oxidant under mild conditions, provides a cost-effective and environmentally benign approach to various β-keto sulfones.
- Yadav, Vinod K.,Srivastava, Vishnu P.,Yadav, Lal Dhar S.
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p. 427 - 431
(2016/02/09)
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- Operando X-ray absorption and EPR evidence for a single electron redox process in copper catalysis
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An unprecedented single electron redox process in copper catalysis is confirmed using operando X-ray absorption and EPR spectroscopies. The oxidation state of the copper species in the interaction between Cu(ii) and a sulfinic acid at room temperature, and the accurate characterization of the formed Cu(i) are clearly shown using operando X-ray absorption and EPR evidence. Further investigation of anion effects on Cu(ii) discloses that bromine ions can dramatically increase the rate of the redox process. Moreover, it is proven that the sulfinic acids are converted into sulfonyl radicals, which can be trapped by 2-arylacrylic acids and various valuable β-keto sulfones are synthesized with good to excellent yields under mild conditions.
- Lu, Qingquan,Zhang, Jian,Peng, Pan,Zhang, Guanghui,Huang, Zhiliang,Yi, Hong,Miller, Jeffrey T.,Lei, Aiwen
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p. 4851 - 4854
(2015/07/27)
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- Synthesis of β-keto-sulfones via metal-free TBAI/TBHP mediated oxidative cross-coupling of vinyl acetates with sulfonylhydrazides
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A novel and efficient protocol for the synthesis of β-keto-sulfone derivatives via TBAI/TBHP mediated oxidative cross-coupling of vinyl acetates with sulfonylhydrazides has been developed.
- Tang, Yucai,Fan, Yuanyuan,Gao, Hongjie,Li, Xiaoqing,Xu, Xiangsheng
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supporting information
p. 5616 - 5618
(2015/09/21)
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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 of N-benzenesulfonamide-1H-pyrazoles bearing arylsulfonyl moiety: Novel celecoxib analogs as potent anti-inflammatory agents
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The reaction of arylsulfones 11a-d with hydrazonoyl chloride derivative 13 furnished celecoxib analogs 4-(3-acetyl-5-aryl-4-(arylsulfonyl)-1H-pyrazol-1-yl) benzenesulfonamides 15a-d, respectively. Oximes 16a, b and hydrazones 17a, b were prepared by reacting sulfones 11a, b with hydroxyl amine and phenyl hydrazine, respectively. The anti-inflammatory activity of the synthesized compounds showed that, 5-(4-bromophenyl)-4-(phenylsulfonyl)pyrazole 15c and 5-(4-bromophenyl)-4-(4-tolylsulfonyl)pyrazole 15d exhibited excellent anti-inflammatory activity with ED50 = 68 ± 2.2 and 51 ± 0.7 μM/kg, respectively, higher than that of celecoxib (ED 50 = 86 ± 1.1 μM/kg) after 3 h with acceptable ulcer index. In addition, the LD50 of 15c and 15d is 7.1 mM/kg for each, and 9.8 mM/kg for celecoxib. Compound 15d appeared selectivity index (COX-2/COX-1) almost the half of celecoxib while 15c is non-selective for COX-2. Compound 15c with ED50 = 80 ± 2.8 μM/kg showed a significant analgesic activity when compared with celecoxib (ED50 = 70 ± 3.9 μM/kg) after 2 h whereas 15b (ED50 = 50 ± 1.2 μM/kg) and 15d (ED50 = 69 ± 2.7 μM/kg) seemed to be more potent than celecoxib (ED50 = 156 ± 4.8 μM/kg) but with a shorter duration (0.5 h).
- Abdel-Aziz, Hatem A.,Al-Rashood, Khalid A.,Eltahir, Kamal Eldin H.,Suddek, Ghada M.
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p. 416 - 422
(2014/05/20)
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- Aerobic oxysulfonylation of alkenes using thiophenols: An efficient one-pot route to β-ketosulfones
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We have developed a highly efficient synthetic route to β-ketosulfones via AgNO3 catalyzed oxysulfonylation of alkenes using thiophenols in the presence of air (O2) and K2S2O8 as eco-friendly oxidants. Thiophenols have been used as sulfonylation precursors for the first time in a dioxygen activation based radical process. Moreover, the protocol also offers a new and convenient method for the synthesis of β-hydroxysulfides at room temperature without the use of any initiator. This journal is
- Singh, Atul K.,Chawla, Ruchi,Keshari, Twinkle,Yadav, Vinod K.,Yadav, Lal Dhar S.
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supporting information
p. 8550 - 8554
(2014/12/10)
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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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- Aerobic oxysulfonylation of alkynes in aqueous media: Highly selective access to β-keto sulfones
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The first application of inexpensive commercially available sulfinate salts to produce β-keto sulfones directly from alkynes via aerobic oxysulfonylation has been developed. It is a highly selective (undesired Glaser-Hay homo-coupling and ATRA process totally suppressed) general method of functionalization of alkynes on water at room temperature involving FeCl 3/K2S2O8 catalyzed formation of sulfonyl radicals from sulfinate salts.
- Singh, Atul K.,Chawla, Ruchi,Yadav, Lal Dhar S.
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p. 2845 - 2848
(2014/05/06)
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- Aerobic oxidation in nanomicelles of aryl alkynes, in water at room temperature
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On the basis of the far higher solubility of oxygen gas inside the hydrocarbon core of nanomicelles, metal and peroxide free aerobic oxidation of aryl alkynes to β-ketosulfones has been achieved in water at room temperature. Many examples are offered that illustrate broad functional group tolerance. The overall process is environmentally friendly, documented by the associated low E Factors. It's all happenin' in the micelle! The highly preferential dissolution of oxygen gas within the lipophilic cores inside nanomicelles leads to efficient trapping of in situ generated vinyl radicals. These intermediate radicals, derived from arylalkynes and sulfinic acids, lead to β-ketosulfone products, formed under especially mild and green conditions: no metals, no heating or cooling, recyclable aqueous media, and low E Factors.
- Handa, Sachin,Fennewald, James C.,Lipshutz, Bruce H.
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supporting information
p. 3432 - 3435
(2014/04/03)
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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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- Chemoselective one-pot synthesis of β-keto sulfones from ketones
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A practical method to synthesize substituted β-keto sulfones directly from ketones at room temperature has been developed. This method involves the nucleophilic addition of a base generated enolate to sulfonyl iodide. The reaction shows high chemoselectivity for the addition of a sulfonyl group to an α-carbon over a hydroxyl group. In addition, the given protocol provides good to excellent yields of β-keto sulfones under mild reaction conditions. Moreover, the regiochemical aspect of the protocol is also explored.
- Rawat, Vikas S.,Reddy, Perla L. M.,Sreedhar, Bojja
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p. 5165 - 5168
(2014/01/23)
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- Copper-catalyzed direct oxysulfonylation of alkenes with dioxygen and sulfonylhydrazides leading to β-ketosulfones
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The first copper-catalyzed oxysulfonylation reaction of alkenes with dioxygen and sulfonylhydrazides for the construction of β-ketosulfones has been developed under mild conditions without any ligand or additive.
- Wei, Wei,Liu, Chunli,Yang, Daoshan,Wen, Jiangwei,You, Jinmao,Suo, Yourui,Wang, Hua
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supporting information
p. 10239 - 10241
(2013/10/22)
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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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- IBX/Imediated reaction of sodium arenesulfinates with alkenes: Facile synthesis of β-keto sulfones
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A direct synthesis of -keto sulfones from alkenes is described. A combination of o-iodoxybenzoic acid/iodine (IBX/I was found to mediate the reactions of alkenes with arenesulfinates to yield -keto sulfones in good yields via a one-pot reaction. Georg Thieme Verlag Stuttgart · New York.
- Samakkanad, Natthapol,Katrun, Praewpan,Techajaroonjit, Thanachart,Hlekhlai, Sornsiri,Pohmakotr, Manat,Reutrakul, Vichai,Jaipetch, Thaworn,Soorukram, Darunee,Kuhakarn, Chutima
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experimental part
p. 1693 - 1699
(2012/07/03)
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- Solid-phase synthesis of β-keto sulfones
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A novel method for the preparation of β-keto-sulfones through the use of organoselenium reagents in the solid phase by polystyrene-supported benzeneselenosulfonate or tolueneseleno-sulfonate with acetylenes has been developed. Georg Thieme Verlag Stuttgart.
- Qian, Hao,Huang, Xian
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p. 1934 - 1936
(2007/10/03)
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- Rapid and convenient synthetic strategy for 2-amino-4-aryl-5-aryl-sulfonyl thiazoles
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Synthesis of 2-amino-4-aryl-5-arylsulfonyl thiazoles 2a-i have been successfully carried out in one pot by condensing α-aryl sulfonyl-4-substituted acetophenones with phenyl trimethyl ammonium tribromide (PTT) and thiourea. The required α-aryl sulfonyl-4-substituted acetophenones have also been prepared by modified one pot method.
- Bhingolikar,Mahalle,Bondge,Mane
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p. 2589 - 2593
(2007/10/03)
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- CHEMICAL COMPOUNDS
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Compounds of formula (I):wherein variable groups are as defined within; for use in the inhibition of 11betaHSD1 are described
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- Synthesis of sulfones from arenesulfonyl chlorides and alkyl halides using the Sm/HgCl2 bimetallic system
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A simple and convenient procedure for the synthesis of sulfones from arenesulfonyl chlorides and alkyl halides using the Sm/HgCl2 bimetallic system in tetrahydrofuran is presented.
- Zhang, Jiming,Zhang, Yongmin
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p. 516 - 517
(2007/10/03)
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- Indium-mediated Coupling Reaction of Sulfonyl Chlorides with Alkyl Bromides in Water. A Facile Synthesis of Sulfones
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Indium-mediated coupling of alkyl bromides with aromatic sulfonyl chlorides gives the corresponding sulfones in aqueous media with moderate to good yields.
- Wang, Lei,Zhang, Yongmin
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p. 588 - 589
(2007/10/03)
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- A convenient synthesis of sulfones using zinc mediated coupling reaction of sulfonyl chlorides with alkyl halides in aqueous media
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An efficient procedure for the preparation of sulfones has been developed through a simple reaction of aromatic sulfonyl chlorides with suitable alkyl halides mediated by commercial zinc powder in aqueous media at 0 °C ~ room temperature.
- Sun, Xinghua,Wang, Lei,Zhang, Yongmin
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p. 1785 - 1791
(2007/10/03)
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- Polyethylene Glycol (PEG) 4000 Catalysed Regioselective Nucleophilic Ring Opening of Oxiranes - A New And Convenient Synthesis of β-Hydroxy Sulfone and β-Hydroxy Sulfide
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Oxiranes and sodium p-toluene sulfinate salt react smoothly in a regioselective manner in the presence of PEG4000 to furnish β-hydroxy sulfone and β-hydroxysulfide.The reaction was extended for the preparation of alkylsulfones and β-oxosulfones from alkylhalide and β-oxohalide respectively.
- Maiti, A. K.,Bhattacharyya, P.
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p. 10483 - 10490
(2007/10/02)
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