cas 61820-95-9, 4'-METHYL-2(P-TOLYL SULFONYL)ACETOPHENONE

Articles about 61820-95-9Total 58 be found

Article title
Article abstract
Author
Journal number and time
Download

Acridine Orange Hemi(Zinc Chloride) Salt as a Lewis Acid-Photoredox Hybrid Catalyst for the Generation of α-Carbonyl Radicals
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,Mandal, Tanumoy,De Sarkar, Suman
p. 755 - 765
(2021/12/10)

Copper-catalyzed aerobic oxidative cross-coupling reactions of vinylarenes with sulfinate salts: A direct approach to β-ketosulfones
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
(2021/01/25)

Photosensitizer-free synthesis of β-keto sulfones: Via visible-light-induced oxysulfonylation of alkenes with sulfonic acids
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
supporting information
p. 4537 - 4541
(2021/05/31)

Building a Pyrazole–Benzothiadiazole–Pyrazole Photosensitizer into Metal–Organic Frameworks for Photocatalytic Aerobic Oxidation
Charge separation plays a crucial role in regulating photochemical properties and therefore warrants consideration in designing photocatalysts. Metal–organic frameworks (MOFs) are emerging as promising candidates for heterogeneous photocatalysis due to their structural designability and tunability of photon absorption. Herein, we report the design of a pyrazole–benzothiadiazole–pyrazole organic molecule bearing a donor–acceptor–donor conjugated π-system for fast charge separation. Further attempts to integrate such a photosensitizer into MOFs afford a more effective heterogeneous photocatalyst (JNU-204). Under visible-light irradiation, three aerobic oxidation reactions involving different oxygenation pathways were achieved on JNU-204. Recycling experiments were conducted to demonstrate the stability and reusability of JNU-204 as a robust heterogeneous photocatalyst. Furthermore, we illustrate its applications in the facile synthesis of pyrrolo[2,1-a]isoquinoline-containing heterocycles, core skeletons of a family of marine natural products. JNU-204 is an exemplary MOF platform with good photon absorption, suitable band gap, fast charge separation, and extraordinary chemical stability for proceeding with aerobic oxidation reactions under visible-light irradiation.
Jin, Ji-Kang,Wu, Kun,Liu, Xin-Yi,Huang, Guo-Quan,Huang, Yong-Liang,Luo, Dong,Xie, Mo,Zhao, Yifang,Lu, Weigang,Zhou, Xiao-Ping,He, Jian,Li, Dan
supporting information
p. 21340 - 21349
(2021/12/17)

Oxy-sulfonylation of terminal alkynesviaC-S coupling enabled by copper photoredox catalysis
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
supporting information
p. 3569 - 3574
(2021/06/06)

Cu(OTf)2-Catalyzed efficient sulfonylation of vinyl azides with sodium sulfinates
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
supporting information
p. 3492 - 3500
(2021/10/14)

Copper-Catalyzed Aerobic Oxidative Cleavage of Unstrained Carbon-Carbon Bonds of 1,1-Disubstituted Alkenes with Sulfonyl Hydrazides
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
supporting information
p. 859 - 865
(2021/03/04)

Metal-Free Electrochemical Coupling of Vinyl Azides: Synthesis of Phenanthridines and β-Ketosulfones
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
p. 6135 - 6145
(2020/10/06)

Preparation method of beta-carbonyl sulfone compound
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.
-
Paragraph 0039-0042; 0043-0046

(2020/12/09)

Biomimetic photocatalytic sulfonation of alkenes to access β-ketosulfones with single-atom iron site
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
supporting information
p. 230 - 237
(2020/01/21)

A Naphthalimide-Based ND-O-EAc Photocatalyst for Sulfonation of Alkenes to Access β-Ketosulfones Under Visible Light
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
supporting information
p. 3456 - 3461
(2020/06/08)

Electrochemical Synthesis of β-Ketosulfones from Switchable Starting Materials
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)

Visible light promoted sulfonylation and sulfonylcarbonylation of alkenes
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
supporting information

(2020/05/26)

Sulfated tungstate/dioxygen: A new catalytic system for oxysulfonylation of styrenes to form β-keto sulfones
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.
p. 10554 - 10561
(2020/07/14)

NBS-mediated synthesis of β-keto sulfones from benzyl alcohols and sodium arenesulfinates
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
supporting information
p. 3479 - 3484
(2019/05/21)

Unprecedented Reactivity of β-Iodovinyl Sulfones: An Efficient Synthesis of β-Keto Sulfones and β-Keto Thiosulfones
An unprecedented reactivity of (E)-β-iodovinyl sulfones in the presence of NaOAc is reported. The (E)-β-iodovinyl sulfones were treated with NaOAc in DMSO/H2O to yield β-keto sulfones in moderate to high yields. A novel oxidative difunctionalization of β-iodovinyl sulfones with thiosulfonates and NaOAc in DMF has been developed. This metal-free oxosulfenylation is an operationally simple to access a wide range of β-keto thiosulfones (α-thioaryl-β-keto sulfones) in moderate to high yields. The transformations were reliable at gram-scale, thus illustrating its efficiency and practicality. A plausible mechanism for the protocol is also proposed.
Reddy, Raju Jannapu,Kumar, Jangam Jagadesh,Kumari, Arram Haritha
p. 3771 - 3775
(2019/06/24)

Heterogeneous copper-catalyzed oxidative coupling of oxime acetates with sodium sulfinates: An efficient and practical synthesis of β-keto sulfones
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
(2019/06/08)

Cu-doped zeolitic imidazolate framework catalysed highly selective conversion of alkynes to β -keto and vinyl sulfones using sodium sulfinates
Abstract: Cu 2 +-doped zeolitic imidazolate framework-8 (ZIF-8)-catalyzed one-pot procedure to synthesize β -keto and vinyl sulfones by the direct oxysulfonylation and hydrosulfonylation of alkynes via radical reaction under mild conditions has been described. The advantages of this protocol included broad substrate scope and excellent β -keto and E-stereoselectivity. The Cu/ZIF-8 catalyst not only exhibited excellent performance but also had a great stability in the reaction, successfully allowing its reuse up to five cycles. This efficient Cu/ZIF-8 heterogeneous catalyst is explored for the first time to generate β -keto and vinyl sulfones. Graphical Abstract:: Cu 2 +-doped zeolitic imidazolate framework-8 (ZIF-8)-catalyzed one-pot procedure to synthesize β -keto and vinyl sulfones by the direct oxysulfonylation and hydrosulfonylation of alkynes via radical reaction under mild conditions is described. The advantages of this protocol included broad substrate scope and excellent β -keto and E-stereoselectivity. This efficient Cu/ZIF-8 heterogeneous catalyst is explored for the first time for C-S bond formation. [Figure not available: see fulltext.].
Yalavarthi, Nageswara Rao,Gundoju, Narayanarao,Bokam, Ramesh,Ponnapalli, Mangala Gowri
(2019/01/11)

Method for synthesizing alpha-sulfone ketone compound from alpha, alpha-dibromo ketone by one-pot process
The invention discloses a method for synthesizing a high-added-value alpha-sulfone ketone compound from an alpha, alpha-dibromo ketone compound by a one-pot process. The method has the advantages thatan alpha-sulfone ketone derivative is synthesized from alpha, alpha-dibromo ketone, which is simple and easy to obtain, by the one-pot process without separation of an alpha-bromo ketone intermediate, so that a separation process for an intermediate product is omitted, the steps are reduced, and requirements for environment protection are met; the steps of the method are simple and easy to operate, no transition metal reagents are required, and economical sulfonate with less pollution is directly used as a promoter and a sulfonating agent for reducing debromination of the alpha, alpha-dibromoketone, so that the cost is reduced, and economic benefits of reactions are increased; a system for preparing the alpha-sulfone ketone derivative by the one-pot process is developed to provide a novel synthesis method for preparation of the alpha-sulfone ketone compound, and the method has good industrialization prospect and potential application value.
-
Page/Page column 10; 11

(2019/10/17)

Visible-light promoted aerobic difunctionalization of alkenes with sulfonyl hydrazides for the synthesis of β-keto/hydroxyl sulfones
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
supporting information
p. 3507 - 3513
(2019/04/14)

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
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.
p. 1 - 9
(2018/04/25)

A metal-free and regioselective approach to (Z)-β-fluorovinyl sulfones and their chemoselective hydrogenation to β-fluoroalkyl sulfones
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
p. 108 - 116
(2018/01/01)

Synthesizing method of beta-keto sulfone compound
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.
-
(2018/09/08)

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
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
p. 3703 - 3705
(2018/09/14)

Copper Triflate Mediated α-Monohalogenation of α-Diazo β-Ketosulfones with Ammonium Halides
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
p. 2045 - 2056
(2017/04/26)

Construction of Sulfonyl Oxabenzo[3.3.1]bicyclic Core via Cyclocondensation of β-Ketosulfones and o-Formyl Allylbenzenes
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
p. 13324 - 13332
(2017/12/26)

Synthesis and antifungal activity of novel oxazolidin-2-one-linked 1,2,3-triazole derivatives
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
p. 2258 - 2262
(2017/12/26)

Photoinduced rearrangement of vinyl tosylates to β-ketosulfones
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
supporting information
p. 3530 - 3534
(2017/08/15)

Method for efficiently synthesizing beta-ketone sulfonyl compounds through visible light induction
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.
-
Page/Page column 7

(2017/07/21)

Preparation method of beta-ketosulfone
The invention discloses a preparation method of beta-ketosulfone. The preparation method of the beta-ketosulfone comprises the steps of adding beta-ketonic acid, N-bromosuccinimide and sodium sulfinate into a reaction test tube, then adding water and sodium phosphate dodecahydrate, and heating to 20 to 25 DEG C for reacting for 12 to 24 hours; after finishing reaction, extracting with ethyl acetate for three times, drying an organic phase with anhydrous sodium sulfate, carrying out vacuum concentration to remove a solvent, and performing silica-gel column chromatography to finally obtain a corresponding product. The problems that during the preparation of the beta-ketosulfone, halohydrocarbon and a pre-functionalized substrate with high toxicity need to be used, and a toxic solvent is used are solved.
-
Paragraph 0044; 0045

(2017/08/31)

Method for synthesizing aryl sulfone compound as pharmaceutical intermediate
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.
-
Paragraph 0036; 0037; 0038; 0039; 0040

(2016/10/24)

Synthesis of (E)-1,4-diaryl-2-butene-1,4-diones
We report a facile route for the preparation of symmetric and unsymmetric (E)-1,4-diaryl-2-butene-1,4-diones 3 by a two-step route, including (1) nucleophilic substitution of 1 with sulfinic acid sodium salts, and (2) K2CO3 mediated alkylation of β-ketosulfones 4 with 1 followed by sequential desulfonylation of the resulting 1,4-diketones 5 in acetone. These products were obtained in high yields.
Chan, Chieh-Kai,Chang, Meng-Yang
p. 390 - 405
(2017/01/29)

Catalyst-Free Difunctionalization of Activated Alkenes in Water: Efficient Synthesis of β-Keto Sulfides and Sulfones
Difunctionalization of activated alkenes, a powerful strategy in chemical synthesis, has been accomplished for direct synthesis of a series of β-keto sulfides and β-keto sulfones. The transformation, mediated by O2, proceeds smoothly in water and without any catalyst. Prominent advantages of this method include mild reaction conditions, purification simplicity, and gram-scale synthesis, underlining the practical utility of this methodology.
Wang, Huamin,Wang, Guangyu,Lu, Qingquan,Chiang, Chien-Wei,Peng, Pan,Zhou, Jiufu,Lei, Aiwen
p. 14489 - 14493
(2016/10/03)

Visible-light initiated direct oxysulfonylation of alkenes with sulfinic acids leading to β-ketosulfones
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
supporting information
p. 5630 - 5634
(2016/10/22)

Visible-light-promoted syntheses of β-keto sulfones from alkynes and sulfonylhydrazides
A variety of functionalized β-keto sulfones were smoothly prepared through oxysulfonylation of commercially available alkynes with sulfonylhydrazides under the synergistic interactions of visible light irradiation, Ru(bpy)3Cl2 photocatalyst, oxygen, KI, and NaOAc basic additive under very mild reaction conditions.
Cai, Shunyou,Chen, Danling,Xu, Yaohui,Weng, Wen,Li, Lihuang,Zhang, Ruijie,Huang, Mingqiang
supporting information
p. 4205 - 4209
(2016/05/24)

Molecular iodine mediated oxidative coupling of enol acetates with sodium sulfinates leading to β-keto sulfones
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.
p. 2236 - 2238
(2016/05/10)

Iron-Catalyzed Oxidative Sulfonylation of Enol Acetates: An Environmentally Benign Approach to β-Keto Sulfones
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.
p. 427 - 431
(2016/02/09)

Synthesis of 2-sulfonyl ketone compound by the method
The invention discloses a method for synthesizing 2-sulfonyl ketone compounds. The method comprises the following steps: mixing substituted N-vinyl acetamide, sulfohydrazide compounds, a catalyst, an oxidant and a solvent to obtain a mixed liquid; and reacting for 2-12 hours at 20-120 DEG C; and then, decompressing to remove the solvent and separating to obtain the 2-sulfonyl ketone compounds, wherein the catalyst is organic amine salt, the oxidant is peroxide and the molar ratio of the sulfohydrazide compound to the substituted N-vinyl acetamide is (1-3):1. The invention provides a new route for synthesizing the 2-sulfonyl ketone compounds. By taking N-vinyl acetamide and the sulfohydrazide compounds as raw materials, the substrate is good in adaptability and corresponding 2-sulfonyl ketone compounds can be synthesized by various substituents. The method is mild in reaction condition, safe and environmental friendly and free from exhaust gases.
-
Paragraph 0066; 0067

(2016/10/08)

Operando X-ray absorption and EPR evidence for a single electron redox process in copper catalysis
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
p. 4851 - 4854
(2015/07/27)

Synthesis of β-keto-sulfones via metal-free TBAI/TBHP mediated oxidative cross-coupling of vinyl acetates with sulfonylhydrazides
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
supporting information
p. 5616 - 5618
(2015/09/21)

Aerobic Nickel-Catalyzed Hydroxysulfonylation of Alkenes Using Sodium Sulfinates
Nickel-catalyzed hydroxysulfonylation of alkenes was achieved using sodium sulfinates under air atmosphere. The procedure enabled the selective synthesis of β-hydroxysulfones in good yields and suppressed the formation of β-ketosulfones. On the contrary, sulfonylation of alkynes with sodium sulfonates afforded only β-ketosulfones.
Taniguchi, Nobukazu
p. 7797 - 7802
(2015/08/18)

Tetrabutylammonium iodide-catalyzed oxidative coupling of enamides with sulfonylhydrazides: Synthesis of β-keto-sulfones
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
p. 7084 - 7090
(2015/06/30)

Synthesis of ionic liquid-supported hypervalent iodine reagent and its application as a 'catch and release' reagent for α-substituted acetophenones
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
p. 14297 - 14303
(2014/04/17)

Effective method of β-keto sulfones synthesis
-
Savka,Pohodylo,Obushak
p. 296 - 297
(2014/04/17)

Aerobic oxysulfonylation of alkenes using thiophenols: An efficient one-pot route to β-ketosulfones
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.
supporting information
p. 8550 - 8554
(2014/12/10)

Copper-catalyzed coupling of oxime acetates with sodium sulfinates: An efficient synthesis of sulfone derivatives
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
supporting information
p. 4205 - 4208
(2014/05/06)

Aerobic oxysulfonylation of alkynes in aqueous media: Highly selective access to β-keto sulfones
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.
p. 2845 - 2848
(2014/05/06)

Silver(I)-mediated reaction of trimethylsilylated arylacetylenes with sulfonyl chlorides: Unexpected formation of vinyl sulfones
A novel reaction of trimethylsilylated arylacetylenes with sulfonyl chlorides was performed in the presence of silver nitrate or triflate. Conjugated vinyl sulfones as dramatic products were obtained in moderate yields and with Z-selectivity. A free radical mechanism has been proposed to account for the formation of the products.
Deng, Gui Sheng,Sun, Teng Fei
p. 1115 - 1118,4
(2020/08/20)

IBX/Imediated reaction of sodium arenesulfinates with alkenes: Facile synthesis of β-keto sulfones
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
experimental part
p. 1693 - 1699
(2012/07/03)

A regioselective catalyst- and additive-free synthesis of β-keto sulfones from aryl acetylenes and sodium arenesulfinates
A facile and regioselective procedure for the preparation of β-keto sulfones has been developed through a simple reaction of aryl acetylenes and sodium arenesulfinates in nitroethane as a solvent at 50°C. The procedure is catalyst- and additive-free and shows a wide range of functional-group tolerance. In this system the formation of new C-O and C-S bonds occurs in a one-pot procedure. Georg Thieme Verlag Stuttgart · New York.
Sreedhar, Bojja,Rawat, Vikas S.
supporting information; experimental part
p. 413 - 417
(2012/03/11)