- Synthesis and x-ray structure of (1 Z,2 Z)-1,2-Bis(2-(phenylsulfonyl)-1-(4-tolyl)ethylidene)hydrazine
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The title compound (1Z,2Z)-1,2-bis(2-(phenylsulfonyl)-1-(4-tolyl)ethylidene)hydrazine (5) was prepared, in 78% yield, by the reaction of 2-(phenylsulfonyl)-1-(4-tolyl)ethan-1-one (3) with hydrazine hydrate in acetic acid at 90°C under microwave irradiatio
- Abdel-Aziz, Hatem A.,Ghabbour, Hazem A.,Al-Rashood, Khalid A.,Fun, Hoong-Kun
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- A glucose oxidase-hemoglobin system for efficient oxysulfonylation of alkenes/alkynes in water
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Background: β-ketosulfones are important bioactive compounds that have been extensively studied in organic chemistry. In this work, a green and efficient process for the synthesis of β-ketosulfones from alkenes (1) or alkynes (3) with sodium benzenesulfinate (2) was developed. Results: Under optimal conditions (alkenes (0.5 mmol) or alkynes (0.5 mmol), sodium benzenesulfinate (0.5 mmol), water (2 mL), hemoproteins (heme concentration: 0.06 mol%), GOX (42 U/ml), room temperature, 2 h), high yields of β-ketosulfones could be obtained when HgbRb (hemoglobin from rabbit blood) and GOX (glucose oxidase from Aspergillus niger) was used as the catalyst. Conclusion: This enzymatic method demonstrates the great potential for the synthesis of β-ketosulfones and extends the application of dual protein systems in organic synthesis.
- Li, Chen,Li, Fengxi,Li, Zhengqiang,Liu, Jiaxu,Su, Jiali,Wang, Chunyu,Wang, Lei,Xu, Yaning,Yu, Yue
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- Chemoenzymatic Oxosulfonylation-Bioreduction Sequence for the Stereoselective Synthesis of β-Hydroxy Sulfones
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A series of optically active β-hydroxy sulfones has been obtained through an oxosulfonylation-stereoselective reduction sequence in aqueous medium. Firstly, β-keto sulfones were synthesized from arylacetylenes and sodium sulfinates to subsequently develop the carbonyl reduction in a highly selective fashion using alcohol dehydrogenases as biocatalysts. Optimization of the chemical oxosulfonylation reaction was investigated, finding inexpensive iron(III) chloride hexahydrate (FeCl3 ? 6H2O) as the catalyst of choice. The selection of isopropanol in the alcohol-water media resulted in high compatibility with the enzymatic process for enzyme cofactor recycling purposes, providing a straightforward access to both (R)- and (S)-β-hydroxy sulfones. The practical usefulness of this transformation was illustrated by describing the synthesis of a chiral intermediate of Apremilast. Interestingly, the development of a chemoenzymatic cascade approach avoided the isolation of β-keto sulfone intermediates, which allowed the preparation of chiral β-hydroxy sulfones in high conversion values (83–94 %) and excellent optical purities (94 to >99 % ee).
- González-Sabín, Javier,Gotor-Fernández, Vicente,López-Agudo, Marina,Lavandera, Iván,Ríos-Lombardía, Nicolás
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- A Compartmentalized-type Bifunctional Magnetic Catalyst for One-pot Aerobic Oxysulfonylation and Asymmetric Transfer Hydrogenation
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Utilization of the confined cavity of the mesoporous silica, the exploration of the synergetic catalysis process for sequential organic transformations has great significance in asymmetric catalysis. In this study, the yolk-shell-structured magnetic nanoparticles with the chiral Ru/diamine species within the nanochannels of the outer mesoporous silica shell and the FeCl3 species on the inner magnet core are fabricated. The electron microscopy images and the structural characterizations disclose the uniformly distributed magnetic nanoparticles with the well-defined single-site ruthenium/diamine active centers onto the outer silica shell. As a yolk-shell-structured bifunctional magnet catalyst, the FeCl3 species enables an efficient aerobic oxysulfonylation between aryl-substituted terminal alkynes and sodium sulfinates to the β-keto sulfones intermediates, and the ruthenium/diamine species sequentially reduces the in-situ generated intermediate to the chiral β-hydroxysulfones products. As we envision, this one-pot aerobic oxysulfonylation/asymmetric transfer hydrogenation process affords various chiral β-hydroxysulfones in high yields with excellent enantioselectivities. Furthermore, this magnetic catalyst can also be conveniently recovered via an additional outer magnet and repeatedly recycled, showing a potential application in industrial interest.
- Wang, Shitong,Wang, Chengyi,Lv, Ning,Tan, Chunxia,Cheng, Tanyu,Liu, Guohua
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p. 909 - 915
(2020/11/30)
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- Oxidative Sulfonylation of Hydrazones Enabled by Synergistic Copper/Silver Catalysis
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A copper/silver-cocatalyzed protocol for oxidative sulfonylation of hydrazones is demonstrated. A wide range of β-ketosulfones and N-acylsulfonamides are directly synthesized in moderate to good yields. Our work provides a viable method for scalable preparation of β-ketosulfone derivatives that have found wide applications in the pharmaceutical industry.
- Xu, Jun,Shen, Chao,Qin, Xian,Wu, Jie,Zhang, Pengfei,Liu, Xiaogang
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p. 3706 - 3720
(2021/02/05)
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- Copper-catalyzed aerobic oxidative cross-coupling reactions of vinylarenes with sulfinate salts: A direct approach to β-ketosulfones
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A copper-catalyzed aerobic oxidative cross-coupling reactions for the synthesis of β-ketosulfones via formation of a C[sbnd]S bond has been demonstrated. Promoted by the crucial copper catalyst, perfect selectivity and good to excellent yields could be achieved. This method, including inexpensive copper catalyst, wide functional group tolerance, and open air conditions, make it very attractive and practical. More importantly, it also provides a versatile tool for the construction of β-ketosulfones from basic starting materials under mild conditions.
- Chen, Yu,Xu, Lei,Wang, Biyu,Jiang, Jingjing,Sun, Yixiang,Li, Longchun
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- 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
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supporting information
p. 464 - 467
(2020/01/31)
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- One-pot synthesis of β-ketosulfones from sulfonyl chloride, hydrazine hydrate and vinyl azide in water
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A novel, facile and efficient strategy for the one-pot synthesis of β-ketosulfones from readily available sulfonyl chloride, hydrazine hydrate and vinyl azides is described. The reaction proceeded very smoothly affording diverse β-ketosulfones in moderate to good yields. This new procedure has the advantages of environmental benign, easy and simple operation, low cost and wide tolerance of functional groups, which provides a highly fascinating protocol to access β-ketosulfones.
- Zhang, Yaohong,Luo, Mengqiang,Li, Yan,Shen, Runfu,Qi, Chenze,Wang, Hai,Cheng, Kai
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supporting information
(2020/10/26)
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- Photo-Mediated Decarboxylative Ketonization of Atropic Acids with Sulfonyl Hydrazides: Direct Access to β-Ketosulfones
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An efficient formation of synthetically and biologically relevant β-ketosulfones via a photo-mediated decarboxylative ketonization of atropic acids was disclosed. The approach features metal-free conditions, good functional group compatibility, readily available starting materials and the use of ubiquitous dioxygen as both oxygen source and oxidant. Furthermore, mechanistic studies reveal that the decarboxylative ketonization reaction proceeds via a radical mechanism and may involve a radical chain reaction. (Figure presented.).
- Chen, Jie,Allyson, Zoe G.,Xin, Jing-Rui,Guan, Zhi,He, Yan-Hong
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supporting information
p. 2045 - 2051
(2020/02/11)
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- Method for preparing β-ketone sulfone compound through visible light-mediated atorvastatin decarboxylation reaction (by machine translation)
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The preparation method of the invention has the characteristics β - that raw materials are simple and easy to obtain, the operation is simple . the reaction conditions are mild, and the reaction system is not sensitive to water . is a method for preparing,ketone sulfone compounds, by using environment-friendly (-source extensive atorvastatin as reactants), and then fully dissolving β -communicating oxygen balloon, in a mixed solvent of acetonitrile and water to obtain, ketal sulphone compounds by reacting, with a stable odorless sulfonyl hydrazide in a mixed solvent of acetonitrile and water under the irradiation of visible light. (by machine translation)
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Paragraph 0152-0157
(2020/04/29)
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- Efficient synthesis of chiral β-hydroxy sulfones: Via iridium-catalyzed hydrogenation
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A highly efficient Ir/f-Amphol-catalyzed asymmetric hydrogenation of prochiral β-keto sulfones was successfully developed to prepare a series of chiral β-hydroxy sulfones with good to excellent results (62%->99% conversions, 35%-99% yields and 86%->99% ee). Our Ir/f-Amphol L4 catalytic system exhibited very high activity; the gram-scale asymmetric hydrogenation was performed well with just 0.005 mol% catalyst loading (S/C = 20,000) to afford the desired product 2a with >99% conversion, 99% yield and 93% ee.
- Tao, Lin,Yin, Congcong,Dong, Xiu-Qin,Zhang, Xumu
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supporting information
p. 785 - 788
(2019/01/30)
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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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- Mukaiyama reagent-promoted metal-free preparation of alkynyl sulfones and phosphonates under mild conditions
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An efficient and mild route for the formation sulfur or phosphor-substituted alkynes was herein demonstrated. The Mukaiyama reagent-mediated transformation started from easily-accessible substrates without carbon-carbon triple bonds, and the reaction proceeded under mild conditions (room temperature) in a one-pot manner, requiring for no transition metal-catalysts. The practical protocol featured for good functional groups tolerance (up to 41 examples) and high efficiency (up to 91% yields) towards alkynyl sulfones and alkynyl phosphonates at low cost.
- Qi, Danyang,Dong, Wanrong,Peng, Zhihong,Zhang, Yingjun,An
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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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- 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; 0082; 0083
(2020/01/03)
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- Preparation method of beta-carbonyl sulfone compound promoted by visible light
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The invention discloses a preparation method of a beta-carbonyl sulfone compound promoted by visible light. The preparation method includes the following steps that olefin and aryl-sulphonazo are mixed with an organic solvent and water, and then a reaction is conducted for 16-24 hours at room temperature under visible illumination; and after the reaction, ethyl acetate is used for extracting reaction liquid, and the beta-carbonyl sulfone compound is obtained after concentration and column chromatography isolation of an extract. According to the method, clean light energy is used as reaction energy, oxygen in air is used as an oxidant and an oxygen source, the beta-carbonyl sulfone compound is effectively synthesized at the room temperature, the method does not require any photocatalyst orequivalent inorganic oxidant, and has the advantages of easy and convenient operation, low energy consumption, high reaction safety, environmental friendliness and the like.
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Paragraph 0120-0123
(2019/11/13)
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- Photocatalyst-Free Visible Light-Induced Synthesis of β-Oxo Sulfones via Oxysulfonylation of Alkenes with Arylazo Sulfones and Dioxygen in Air
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A catalyst-free strategy has been established for the synthesis of β-oxo sulfones via visible light-induced oxysulfonylation of alkenes with arylazo sulfones with dioxygen in air. The present photoinduced transformation proceeds smoothly at room temperature in the absence of an external photosensitizer, which not only provides a mild and efficient approach to various β-oxo sulfones, but also opens a different reaction mode for the photochemical reaction of arylazo sulfones.
- Liu, Qishun,Liu, Fei,Yue, Huilan,Zhao, Xiaohui,Li, Jiangsheng,Wei, Wei
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supporting information
p. 5277 - 5282
(2019/11/16)
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- K2S2O8-mediated decarboxylative oxysulfonylation of cinnamic acids: A transition-metal-free synthesis of β-keto sulfones
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A new paradigm of the oxidative decarboxylative sulfono functionalization of cinnamic acids with sulfinate salts mediated by K2S2O8 under aerobic conditions to afford synthetically and biologically relevant β-keto sulfones has been described. It is the first report on the transition-metal-free synthesis of β-keto sulfones from cinnamic acids, which employs environmentally benign, readily available and inexpensive starting materials and oxidants, viz. air and K2S2O8.
- Chawla,Kapoor, Ritu,Yadav, Lal Dhar S.
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supporting information
(2019/07/30)
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- Switching of Sulfonylation Selectivity by Nature of Solvent and Temperature: The Reaction of β-Dicarbonyl Compounds with Sodium Sulfinates under the Action of Iron-Based Oxidants
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Selectivity of sulfonylation of β-keto esters with sodium sulfinates under the action of iron(III) salts as oxidants can be regulated by the type of solvent used and the reaction temperature. α-Sulfonyl β-keto esters are obtained when the process is conducted in THF/H2O solution at 40 °C. The change of the solvent to iPrOH/H2O and refluxing of a reaction mixture provides α-sulfonyl esters – the products of successive sulfonylation-deacylation. When β-diketones are applied as starting materials, only α-sulfonyl ketones are formed. The reaction pathway includes sulfonylation of dicabonyl compounds under the action of Fe(III) to form α-sulfonylated dicarbonyl compounds, which are then attacked by a solvent as the nucleophile, resulting in the products of successive sulfonylation-deacylation. Participation of the solvent in the reaction pathway determines the products structure.
- Mulina, Olga M.,Pirgach, Dmitry A.,Nikishin, Gennady I.,Terent'ev, Alexander O.
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p. 4179 - 4188
(2019/05/08)
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- Cu-doped zeolitic imidazolate framework catalysed highly selective conversion of alkynes to β -keto and vinyl sulfones using sodium sulfinates
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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
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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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- N-bromosuccinimide mediated decarboxylative sulfonylation of β-keto acids with sodium sulfinates toward β-keto sulfones: Evaluation of human carboxylesterase 1 activity
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A N-bromosuccinimide (NBS) mediated decarboxylative sulfonylation of β-keto acids with sodium sulfinates is developed. The transformation exhibits a broad substrate scope and good functional group tolerance. Preliminary mechanistic studies showed that this reaction is likely to proceed through a nucleophilic substitution of β-keto acid with sulfonyl bromide pathway. All synthesized β-keto sulfones were evaluated the inhibitory effect against human carboxylesterase 1 (CES1). This investigation offers an expedient strategy for efficient synthesis of β-keto sulfones that are widely present in biologically active natural products and pharmaceutical agents.
- Han, Fuzhong,Su, Bobo,Song, Peifang,Wang, Yaqiao,Jia, Lina,Xun, Shanshan,Hu, Minggang,Zou, Liwei
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p. 5908 - 5913
(2018/08/29)
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- An efficient access to β-ketosulfones: Via β-sulfonylvinylamines: Metal-organic framework catalysis for the direct C-S coupling of sodium sulfinates with oxime acetates
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A copper-based framework Cu2(OBA)2(BPY) was synthesized and used as a recyclable heterogeneous catalyst for the synthesis of β-sulfonylvinylamines from sodium sulfinates and oxime acetates via direct C-S coupling reaction. The transformation was remarkably affected by the solvent, and chlorobenzene emerged as the best option. This Cu-MOF displayed higher activity than numerous conventional homogeneous and MOF-based catalysts. The catalyst was reutilized many times in the synthesis of β-sulfonylvinylamines without considerably deteriorating in catalytic efficiency. These β-sulfonylvinylamines were readily converted to the corresponding β-ketosulfones via a hydrolysis step with aqueous HCl solution. To the best of our knowledge, this direct C-S coupling reaction to achieve β-sulfonylvinylamines was not previously conducted with a heterogeneous catalyst.
- To, Tuong A.,Tran, Chau B.,Nguyen, Ngoc T. H.,Nguyen, Hai H. T.,Nguyen, Anh T.,Phan, Anh N. Q.,Phan, Nam T. S.
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p. 17477 - 17485
(2018/05/29)
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- Manganese(III)-Mediated and -Catalyzed Decarboxylative Hydroxysulfonylation of Arylpropiolic Acids with Sodium Sulfinates in Water
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With water as both solvent and reactant, a novel manganese(III)-mediated and -catalyzed synthesis of β-ketosulfones through decarboxylative hydroxysulfonylation reactions of arylpropiolic acids with sodium sulfinates is described. This protocol has the advantages of mild reaction conditions, short reaction time, easy to handle reagents, purification simplicity, and being environmentally benign, which demonstrate the practical utility of this methodology. (Figure presented.).
- Xiong, Yan-Shi,Weng, Jiang,Lu, Gui
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supporting information
p. 1611 - 1616
(2018/03/05)
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- Metal-free tetra-n-butylammonium bromide-mediated aerobic oxidative synthesis of β-ketosulfones from styrenes
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An efficient and broadly applicable protocol for the aerobic coupling of styrenes with sulfonylhydrazides has been developed that affords β-ketosulfones bearing various functional groups in moderate to excellent yields. The preliminary experimental results support the involvement of active benzyl radical species, and a radical pathway was therefore proposed for the reaction.
- Wan, Xin,Sun, Kai,Zhang, Guisheng
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p. 353 - 357
(2017/03/13)
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- Synthesis of β-Keto Sulfones via Coupling of Aryl/Alkyl Halides, Sulfur Dioxide and Silyl Enolates through Metal-Free Photoinduced C–X Bond Dissociation
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A photoinduced sulfonylative coupling of aryl/alkyl halides, DABCO?(SO2)2 (1,4-diazabicyclo[2.2.2]octane-sulfur dioxide), and silyl enolates under metal-free conditions has been developed, giving rise to β-keto sulfones in good yields. This transformation proceeds smoothly at room temperature under ultraviolet irradiation with good tolerance of various functional groups. Aryl iodides/bromides and alkyl halides are all good substrates in the sulfonylative reaction. A plausible mechanism is proposed, which proceeds through a radical process under photoinduced conditions. (Figure presented.).
- Gong, Xinxing,Ding, Yechun,Fan, Xiaona,Wu, Jie
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supporting information
p. 2999 - 3004
(2017/09/08)
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- Visible-light initiated direct oxysulfonylation of alkenes with sulfinic acids leading to β-ketosulfones
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Visible light along with 1 mol% eosin Y catalyzed the direct oxysulfonylation of alkenes with sulfinic acids via a photoredox process which has been developed at room temperature under transition-metal-free conditions. The present reaction provides a highly efficient approach to diverse β-ketosulfones in moderate to good yields. It should provide a promising synthesis candidate for the formation of diverse and useful β-ketosulfone derivatives in the fields of synthetic and pharmaceutical chemistry.
- Yang, Daoshan,Huang, Ben,Wei, Wei,Li, Jin,Lin, Gu,Liu, Yaru,Ding, Jiehua,Sun, Pengfei,Wang, Hua
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supporting information
p. 5630 - 5634
(2016/10/22)
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- Oxysulfonylation of Alkenes with Sulfonyl Hydrazides under Transition-Metal-Free Conditions
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A novel method to synthesise β-keto sulfones is demonstrated by Br?nsted acid promoted oxysulfonylation of alkenes with sulfonyl hydrazides under transition-metal-free conditions. The reaction selectively affords structurally diverse β-keto sulfones in good to excellent yields in a 9:1 mixture of acetonitrile/water.
- Liu, Congrong,Ding, Lianghui,Guo, Guang,Liu, Weiwei
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supporting information
p. 910 - 912
(2016/03/01)
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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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- O2-mediated C(sp2)-X bond oxygenation: Autoxidative carbon-heteroatom bond formation using activated alkenes as a linkage
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Autoxidative carbon-heteroatom bond formation using activated alkenes as a linkage is described. Heteroatom (O, S) nucleophiles could be transformed into different kinds of valuable β-keto compounds via an O2-mediated C(sp2)-X bond oxygenation process, without using any external organic oxidants or metal catalysts. This journal is
- Lu, Qingquan,Chen, Jiyong,Liu, Chao,Huang, Zhiyuan,Peng, Pan,Wang, Huamin,Lei, Aiwen
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p. 24494 - 24498
(2015/03/30)
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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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- Iron-catalyzed direct difunctionalization of alkenes with dioxygen and sulfinic acids: A highly efficient and green approach to β-ketosulfones
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A novel iron-catalyzed direct difunctionalization of alkenes with sulfinic acids and dioxygen for the synthesis of β-ketosulfones has been developed under mild conditions. The present protocol, which utilizes an inexpensive iron salt as the catalyst, readily available benzenesulfinic acids as the sulfonylating reagents, and dioxygen as the oxidant and oxygen source, provides a cost-effective and environmentally benign approach to access various β-ketosulfones.
- Wei, Wei,Wen, Jiangwei,Yang, Daoshan,Wu, Min,You, Jinmao,Wang, Hua
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supporting information
p. 7678 - 7681
(2014/12/10)
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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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- K2S2O8-mediated aerobic oxysulfonylation of olefins into β-Keto sulfones in aqueous media
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β-Keto sulfones were obtained in good to excellent yields (73-94%) directly from unactivated olefins by employing inexpensive sodium arenesulfinate salts as sulfonylating agents and K2S2O8 as a radical initiator in open flasks and aqueous media at room temperature under transition-metal-free conditions. The reported oxidative sulfonylation protocol is highly practical and environmentally benign, as self-manifested by the extremely mild reaction conditions. Copyright
- Chawla, Ruchi,Singh, Atul K.,Yadav, Lal Dhar S.
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supporting information
p. 2032 - 2036
(2014/04/17)
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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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- Dioxygen-triggered oxidative radical reaction: Direct aerobic difunctionalization of terminal alkynes toward β-keto sulfones
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An unprecedented dioxygen-triggered oxidative radical process was explored using dioxygen as the solely terminal oxidant, realizing aerobic oxidaitve difunctionalization of terminal alkynes toward β-keto sulfones with high selectivity. Operando IR experiments revealed that pyridine not only acts as a base to successfully surpress ATRA (atom transfer radical addition) process, but also plays a vital role in reducing the activity of sulfinic acids.
- Lu, Qingquan,Zhang, Jian,Zhao, Ganglu,Qi, Yue,Wang, Huamin,Lei, Aiwen
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supporting information
p. 11481 - 11484
(2013/09/02)
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- Multicomponent reactions of β-ketosulfones and formaldehyde in a bio-based binary mixture solvent system composed of meglumine and gluconic acid aqueous solution
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A mixture of two bio-based chemicals, meglumine and gluconic acid aqueous solution (GAAS, 50 wt%), was demonstrated to be a task-specific bio-based solvent for performing the hydroxymethylation of β-ketosulfones with formaldehyde. The formed hydroxymethylation product could further react with a nucleophile, which allowed us to develop some one-pot, stepwise, three-component reactions of β-ketosulfones and formaldehyde in this binary mixture. Particularly, a one-pot, two-step, sequential four-component reaction of α-bromo ketone, sodium benzenesulfinate, thiophenol and formaldehyde was also developed. These results not only demonstrate that it is possible to develop a new bio-based system by mixing two or more bio-based chemicals together, but also confer us a convenient means for controlling the selectivity of some multicomponent reactions of formaldehyde. Because GAAS and meglumine are both highly hydrophilic, the mixed solvent system could thus be recovered after extraction of organic products. In a three-component reaction of β-ketosulfone, paraformaldehyde and α-methylstyrene, the GAAS/meglumine system could be reused at least four times without significant loss of activity. Copyright
- Yang, Jie,Li, Haoquan,Li, Minghao,Peng, Jiajian,Gu, Yanlong
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supporting information; experimental part
p. 688 - 700
(2012/04/23)
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- A regioselective catalyst- and additive-free synthesis of β-keto sulfones from aryl acetylenes and sodium arenesulfinates
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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.
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supporting information; experimental part
p. 413 - 417
(2012/03/11)
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- Silver(I)-mediated reaction of trimethylsilylated arylacetylenes with sulfonyl chlorides: Unexpected formation of vinyl sulfones
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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
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p. 1115 - 1118,4
(2020/08/20)
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- Oxidation of aromatic compounds: XVI. Radical cations derived from acetylenic compounds with electron-withdrawing groups: Reactions and ESR parameters
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One-electron oxidation of aryl-substituted acetylenes ArC≡CX where X is an electron-withdrawing group gives different products, depending on the X substituent. Acetylenic substrates with medium-strength electron-withdrawing substituents, X = CO2/sub
- Vasil'ev,Aristov,Fukin,Kozhanov,Bubnov,Cherkasov
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experimental part
p. 791 - 802
(2009/06/21)
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- β-Keto sulfones as inhibitors of 11β-hydroxysteroid dehydrogenase type I and the mechanism of action
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The design, synthesis, and biological evaluation of β-keto sulfones as 11β-HSD1 inhibitors and the mechanism of inhibition are described here. This class of compounds is not active against 11β-HSD2 and therefore may have therapeutic potential for metabolic syndrome and type 2 diabetes.
- Xiang, Jason,Ipek, Manus,Suri, Vipin,Tam, May,Xing, Yuzhe,Huang, Nelson,Zhang, Yanling,Tobin, James,Mansour, Tarek S.,McKew, John
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p. 4396 - 4405
(2008/03/12)
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- Facile polyethylene glycol (PEG-400) promoted synthesis of β-ketosulfones
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An efficient and convenient synthesis of β-ketosulfones is described. Reaction of an α-haloketone with sodium alkyl/aryl sulphinate yields the corresponding β-ketosulfone promoted by polyethylene glycol (PEG-400) as an efficient reaction medium.
- Suryakiran,Reddy, T. Srikanth,Ashalatha,Lakshman,Venkateswarlu
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p. 3853 - 3856
(2007/10/03)
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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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- A facile one-pot synthesis of β-keto sulfones from ketones under solvent-free conditions
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An easy solvent-free method is described for the conversion of ketones into β-keto sulfones in high yields that involves the in situ generation of α-tosyloxyketones, followed by nucleophilic substitution with sodium arene sulfinate in the presence of tetra-butylammonium bromide at room temperature. The salient features of this one-pot protocol are short reaction times, cleaner reaction profiles, and simple work-up that precludes the use of toxic solvents.
- Kumar, Dalip,Sundaree, Swapna,Rao,Varma, Rajender S.
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p. 4197 - 4199
(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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- Hypervalent iodine in synthesis. 66. One pot preparation of β-keto sulfones by reaction of ketones, [hydroxy(tosyloxy) iodo] benzene, and sodium sulfinates
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One pot reactions of ketones, [hydroxy(tosyloxy)iodo] benzene and sodium sulfinates lead to the formation of the corresponding β-keto sulfones under mild conditions and in good yield.
- Xie,Chen
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p. 3145 - 3149
(2007/10/03)
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