- High Chemoselectivity in the Construction of Aryl Methyl Sulfones via an Unexpected C-S Bond Formation between Sulfonylhydrazides and Dimethyl Phosphite
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A highly chemoselective route to aryl methyl sulfones via an unexpected C S bond formation between sulfonylhydrazides and dimethyl phosphite catalyzed by NaI under mild conditions has been established. This transformation provides an alternative and metal-free pathway to acquire various aryl methyl sulfones in good to excellent yields. Notably, dimethyl phosphite was employed as a stable and readily available alkyl source.
- Liu, Teng,Yu, Shiwen,Shen, Xiang,Li, Yixian,Liu, Jianjun,Huang, Chao,Cheng, Feixiang
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p. 153 - 160
(2021/10/04)
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- Flow Electrosynthesis of Sulfoxides, Sulfones, and Sulfoximines without Supporting Electrolytes
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An efficient electrochemical flow process for the selective oxidation of sulfides to sulfoxides and sulfones and of sulfoxides toN-cyanosulfoximines has been developed. In total, 69 examples of sulfoxides, sulfones, andN-cyanosulfoximines have been synthesized in good to excellent yields and with high current efficiencies. The synthesis was assisted and facilitated through a supporting electrolyte-free, fully automated electrochemical protocol that highlights the advantages of flow electrolysis.
- Amri, Nasser,Wirth, Thomas
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p. 15961 - 15972
(2021/07/20)
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- Switchable Synthesis of Aryl Sulfones and Sulfoxides through Solvent-Promoted Oxidation of Sulfides with O2/Air
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A practical and switchable method for the synthesis of aryl sulfones and sulfoxides via sulfide oxidation was developed. The chemoselectivities of products were simply controlled by reaction temperature using O2/air as the terminal oxidant and oxygen source. The broad substrate scope, easy realization of gram-scale production, and the simplification of a sulfide oxidation system render the strategy attractive and valuable.
- Cheng, Zhen,Sun, Pengchao,Tang, Ailing,Jin, Weiwei,Liu, Chenjiang
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supporting information
p. 8925 - 8929
(2019/11/14)
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- A novel synthesis of aryl methyl sulfones and β-hydroxysulfones from sodium sulfinates and di-tert-butyl peroxide in H2O medium
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A novel and convenient synthetic route for aryl methyl sulfones and β-hydroxysulfones was developed via the radical reaction between sodium sulfinates and di-tert-butyl peroxide (DTBP). Without any catalysts and additives, the synthetic process could be smoothly carried out to afford the target products in good to excellent yields in H2O medium, demonstrating its promising application. In the present system, H2O could act not only as a green solvent but also as a reactant.
- Lai, Junyi,Yuan, Gaoqing
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supporting information
p. 524 - 527
(2018/01/10)
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- An Efficient Oxidation of Sulfides to Sulfones with Urea-Hydrogen Peroxide in the Presence of Phthalic Anhydride in Ethyl Acetate
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A metal-free, environmentally benign oxidation of substituted sulfides directly to their corresponding sulfones is described. Using urea-hydrogen peroxide and phthalic anhydride in ethyl acetate clean conversion into the sulfone was achieved without observation of the possible sulfoxide oxidation product.
- Lutz, Marlon,Wenzler, Marta,Likhotvorik, Igor
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supporting information
p. 2231 - 2234
(2018/04/16)
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- Bovine serum albumin-cobalt(II) Schiff base complex hybrid: An efficient artificial metalloenzyme for enantioselective sulfoxidation using hydrogen peroxide
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An artificial metalloenzyme (BSA-CoL) based on the incorporation of a cobalt(ii) Schiff base complex {CoL, H2L = 2,2′-[(1,2-ethanediyl)bis(nitrilopropylidyne)]bisphenol} with bovine serum albumin (BSA) has been synthesized and characterized. Attention is focused on the catalytic activity of this artificial metalloenzyme for enantioselective oxidation of a variety of sulfides with H2O2. The influences of parameters such as pH, temperature, and the concentration of catalyst and oxidant on thioanisole as a model are investigated. Under optimum conditions, BSA-CoL as a hybrid biocatalyst is efficient for the enantioselective oxidation of a series of sulfides, producing the corresponding sulfoxides with excellent conversion (up to 100%), chemoselectivity (up to 100%) and good enantiomeric purity (up to 87% ee) in certain cases.
- Tang, Jie,Huang, Fuping,Wei, Yi,Bian, Hedong,Zhang, Wei,Liang, Hong
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p. 8061 - 8072
(2016/06/06)
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- In situ-generated chiral iron complex as efficient catalyst for enantioselective sulfoxidation using aqueous H2O2 as oxidant
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A series of amino alcohol-derived, Schiff-base ligands L1-L4 were synthesised and characterized. Iron complexes of these ligands [FeL1(acac)], [FeL2(acac)], [FeL3(acac)] and [FeL4(acac)] were generated in situ to catalyze the asymmetric oxidation of prochiral sulfides using aqueous H2O2 as a terminal oxidant. One of these complexes [FeL1(acac)] was identified as a very efficient catalyst for the enantioselective oxidation of a series of alkyl aryl sulfides with excellent enantioselectivity (75-96% ee), conversion (up to 92%) and chemo selectivity (up to 98%). During the optimization process, a series of electron-donating benzoic acid derivatives were found to favour both conversion and enantioselectivity.
- Bera, Prasanta Kumar,Kumari, Prathibha,Abdi, Sayed H. R.,Khan, Noor-Ul H.,Kureshy, Rukhsana I.,Subramanian,Bajaj, Hari C.
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p. 61550 - 61556
(2015/02/19)
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- A molybdenum based metallomicellar catalyst for controlled and selective sulfoxidation reactions in aqueous medium
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A surfactant based molybdenum system that exhibits catalytic activity for sulfoxidation reactions of various organic sulfides in aqueous medium has been developed and comprehensively characterized using IR, XRD, NMR, ESI-MS, DLS and TEM. The catalyst showcases remarkable selectivity for the preparation of both sulfoxides and sulfones in the range of good to excellent yields. Furthermore, the catalyst showed a high degree of tolerance towards various sensitive functional groups such as hydroxyl, acetal, aldehyde, amine, imine, oxime, cyano and alkene. the Partner Organisations 2014.
- Chakravarthy, Rajan Deepan,Ramkumar, Venkatachalam,Chand, Dillip Kumar
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p. 2190 - 2196
(2014/04/17)
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- A magnetically recyclable Fe3O4@SiO2/Mn(III) chiral salen complex as a highly selective and versatile heterogeneous nanocatalyst for the oxidation of olefins and sulfides
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In this study, a new magnetically recoverable heterogeneous Mn(iii) nanocatalyst (MHMC) was developed by covalent grafting of a homogeneous chiral Mn(iii) salen complex (HMC) onto the surface of a Fe3O4/SiO2 core-shell. The structural and chemical nature of MHMC was characterized by different techniques. The catalytic activity of the MHMC and comparison with its homogeneous analogue were studied for the enantioselective epoxidation of various alkenes to epoxide compounds using tert-butyl hydroperoxide (TBHP) as an oxidant. The MHMC showed higher enantioselectivity and comparable catalytic reactivity to its homogeneous analogue with benefits such as facile recovery and recycling of the heterogeneous catalyst. The results showed that a higher enantioselectivity and yield were observed in the presence of N-methylmorpholine N-oxide (NMNO). The catalytic activity of this complex was also tested in the oxidation of sulfides using aqueous 30% H2O2 in excellent yields. The catalyst was reused for several runs without significant loss in activity and selectivity.
- Allahresani, Ali,Nasseri, Mohammad Ali
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p. 60702 - 60710
(2015/02/19)
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- Development of the large-scale preparation of 2-(Methanesulfonyl) benzenesulfonyl chloride
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A practical and scalable process is described for the preparation of 2-(methansulfonyl)benzenesulfonyl chloride, a key building block used in the synthesis of several drug candidates. The material is prepared by an efficient four-step sequence from inexpe
- Meckler, Harold,Herr, R. Jason
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p. 550 - 555
(2012/08/07)
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- Supramolecular assembly of chiral polyoxometalate complexes for asymmetric catalytic oxidation of thioethers
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In this paper, a chiral amphiphilic cation with two stereocenters has been employed to encapsulate a well-known catalytically activated sandwich-type polyoxometalate, Na12[WZn3(H2O) 2(ZnW9O34)2], through electrostatic interaction. The prepared chiral organic cation-encapsulated polyoxometalate complexes were found to self-aggregate into spherical supramolecular assemblies with a diameter of ca. 100 nm in the reaction solution. These assemblies, serving as microreactors, exhibited an efficient asymmetric catalytic activity for the oxidation of sulfide with up to 72% enantiomeric excess. The coverage density of chiral organic cations enwrapped on the polyoxometalate surface was proved to have an important influence on the enantioselectivity. Detailed kinetic study of the catalytic process showed that the enantioselectivity of sulfide oxidation was derived from the combination of an ineffective asymmetric sulfoxidation and an effective kinetic resolution of the sulfoxide. The present research strategically offers an understanding for the direct and efficient construction of polyoxometalate based supramolecular catalysts for asymmetric reactions through controlling the surface microenvironment.
- Wang, Yizhan,Li, Haolong,Qi, Wei,Yang, Yang,Yan, Yi,Li, Bao,Wu, Lixin
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p. 9181 - 9188
(2013/01/13)
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- Silica-supported molybdenum complex: A novel, selective and reusable organic-inorganic hybrid catalyst for eco-friendly oxidation of sulfides and olefins
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A novel, highly efficient and reusable molybdenum based catalyst has been synthesized by covalent grafting of 2,6-diacetylpyridine-monosalicyloylhydrazone onto functionalized silica followed by complexation with MoO 2(acac)2, and the resulting organic-inorganic hybrid material was found to be highly effective catalyst for oxidation of various sulfides and olefins to their corresponding sulfoxides/sulfones and epoxides, respectively. The catalyst was characterized by elemental analysis (CHN), diffuse reflectance UV-Vis, 13C CPMAS NMR spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM) and BET surface area analysis, energy dispersive X-ray fluorescence (ED-XRF), Fourier-transform infrared (FT-IR) and atomic absorption spectroscopy (AAS). Mild reaction conditions, high turnover frequency, high selectivity, easy recovery and reusability of the catalyst render the present protocol very useful to address the industrial needs and environmental concerns.
- Sharma,Pandey, Amit,Gulati, Shikha
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- Polystyrene supported Al(OTf)3: A stable, efficient, selective, and reusable catalyst for sulfonylation of arenes with sulfonic acids
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Cross-linked polystyrene supported aluminium triflate (Ps-Al(OTf) 3) was found to be an efficient and chemoselective heterogeneous Lewis acid catalyst for the direct conversion of arenes to sulfones using sulfonic acids as sulfonylating agents. The solid acid catalyst is stable (as a bench top catalyst) and can be easily recovered and reused without appreciable change in its efficiency.
- Boroujeni, Kaveh Parvanak
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experimental part
p. 1887 - 1890
(2010/11/18)
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- Tetra-(tetraalkylammonium)octamolybdate catalysts for selective oxidation of sulfides to sulfoxides with hydrogen peroxide
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Tetra-(tetraalkylammonium)octamolybdate catalysts are successfully applied in the selective oxidation of various sulfides to sulfoxides with 30% aqueous hydrogen peroxide as oxidant under mild reaction conditions in 94-100% yield and 95-100% selectivity. The octamolybdate catalysts show high catalytic activity in a high ratio of substrate to catalyst (up to 10000:1) and are recyclable, with actively functional groups, including hydroxyl group and CC bonds, tolerated in the oxidation. The Royal Society of Chemistry 2009.
- Yang, Chuanbo,Jin, Qingping,Zhang, Hua,Liao, Jian,Zhu, Jin,Yu, Bin,Deng, Jingen
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supporting information; experimental part
p. 1401 - 1405
(2010/05/02)
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- Asymmetric oxidation of sulfides under solvent-free or highly concentrated conditions
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The aluminium(salalen) complex was found to be an efficient catalyst for the asymmetric oxidation of sulfides under solvent-free or highly concentrated conditions, in which an only 0.002-0.01 mol% catalyst loading was sufficient to obtain optically active sulfoxides in high yield with high enantioselectivity. The Royal Society of Chemistry.
- Matsumoto, Kazuhiro,Yamaguchi, Tetsufumi,Katsuki, Tsutomu
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p. 1704 - 1706
(2008/12/22)
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- Total Synergistic effect between triflic acid and bismuth(IIIr antimony(III) chlorides in catalysis of the Methanesulfonylation of Arenes
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A total synergistic effect between bismuth(III) or antimony(III) chlorides and triflic acid has been observed in the Friedel-Crafts methanesulfonylation of arenes and has resulted in the development of the first efficient catalytic systems usable for the methanesulfonylation of both activated and deactivated arenes. A proposed mechanism to explain the observed effects is also discussed. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
- Peyronneau, Magali,Boisdon, Marie-Therese,Roques, Nicolas,Mazieres, Stephane,Le Roux, Christophe
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p. 4636 - 4640
(2007/10/03)
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- Sulfur containing compounds
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This invention is directed to novel and known stufur containing compounds and pharmaceutically acceptable salts thereof that have utility as antifungals and as antiproliferative agents against mammalian cells, in particular cancer cells and most particularly leukemia-derived cells. The invention provides a method for synthesizing certain of the sulfur containing compounds that is more efficient than previously known methods.
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Page/Page column 25
(2010/11/30)
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- Friedel-Crafts sulfonylation of aromatics catalysed by solid acids: An eco-friendly route for sulfone synthesis
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A mild and efficient catalytic method for Friedel-Crafts sulfonylation of arenes to the corresponding sulfones using a catalytic amount of reusable solid acid and arene- or alkanesulfonyl chlorides, sulfonic anhydrides and sulfonic acids as sulfonylating agents is described. Solid acids enable formation of a sulfone by the reaction of a sulfonic acid and an arene for the first time. In pursuit of the development of the best catalytic system, various metal-exchanged K10 montmorillonites and synthetic zeolites such as zeolite beta, zeolite Y and ZSM-5 have been screened for Friedel-Crafts sulfone synthesis. Fe3+-montmorillonite in the family of clays and zeolite beta in the family of zeolites exhibit higher activity. The activity is correlated to the presence of the right mix of Bronsted and Lewis acidic sites. The regioselective sulfonylation of toluene and naphthalene are studied in which para and beta selectivities are observed respectively. The Royal Society of Chemistry 2000.
- Choudary, Boyapati M.,Chowdari, N. Sreenivasa,Kantam, M. Lakshmi
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p. 2689 - 2693
(2007/10/03)
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- New and more potent antifungal bisulfides
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From a design principle described in an earlier paper, a new series of substituted aryl methyl disulfides have been prepared and tested against Aspergillus niger and Aspergillus flavus. Methyl p-nitrophenyl disulfide is more potent (by an order of magnitude) than the fungitoxic natural product (CH3SCH2S)2. With the present rationale in hand, one can anticipate which Polycarpamine is an effective antifungal agent. CSIRO 2000.
- Baerlocher, Felix Jakob,Baerlocher, Mark Otto,Langler, Richard Francis,MacQuarrie, Stephanie Lee,Marchand, Maurice Emile
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- Reactions of Arylsulphonyl, Arylthio and Acyl Acetates with S-Containing Heterocumulenes
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The reaction of arylsulphonyl- or (phenylthio)-acetates 1 with carbon disulphide in a basic medium led to the corresponding ketene dithioacetals 2 in good yields.The o-chloro derivative 1d gave with carbon disulphide various products under different reaction conditions.However, the reaction of 1 with phenyl isothiocyanate primarily resulted in N-substituted pyrimidone derivatives 9, except for 1e which mainly gave S,N-analogues of dithioacetals 10e and 10f. β-Ketoesters 1g, h also reacted with phenyl isothiocyanate to afford 5-acyl-2-thioxo-4-pyrimidones 9g, h.The dependency of the polarisation of the double bond in ketene dithioacetals and their S,N-analogues on acceptor groups was investigated with the help of 13C NMR spectroscopy.
- Chatterjee, Swapan K.,Rudorf, Wolf-Dieter
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p. 2916 - 2935
(2007/10/02)
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- The Friedel-Crafts Type Methanesulfonylation of Deactivated Benzenes
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The participation of nonionic donor-acceptor complex was suggested by the analyses of product isolated in the Friedel-Crafts reaction of m-dichlorobenzene with CH3SO2Cl in the presence of AlCl3.On the basis of these observations a new practical method of methanesulfonylation of deactivated benzenes employing methanesulfonic anhydride and CF3SO3H was developed.
- Ono, Mitsunori,Nakamura, Yoshisada,Sato, Shingo,Itoh, Isamu
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p. 395 - 398
(2007/10/02)
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- Process for the nucleophilic substitution of unactivated aromatic and heteroaromatic substrates
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The nucleophilic substitution upon unactivated monocyclic or polycyclic aromatic or heteroaromatic substrates bearing suitable leaving groups can be achieved by catalyzing the substitution of said leaving groups by an anionic nucleophile with a cyclic or acyclic polydentate chelating ligand. Specific products of this reaction can be used in preparing sulfonylurea herbicides.
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- Process for the preparation of aryl alkyl sulfones and aryl vinyl sulfones
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The present invention provides a process for the preparation of aryl alkyl sulfones and aryl vinyl sulfones. The process comprises reacting an aryl compound with an alkyl sulfonyl fluoride or with a vinyl sulfonyl fluoride in the presence of a catalyst selected from AlCl3 and AlBr3. The aryl compound is preferably selected from chlorobenzene, the isomeric xylenes, the isomeric trimethyl benzenes, and mixtures thereof. The alkyl group of the alkyl sulfonyl fluoride preferably contains 1-18 carbon atoms, and the vinyl group of the vinyl sulfonyl fluoride is unsubstituted or substituted with one or more alkyl groups containing 1-5 carbon atoms. The reaction is conducted at a temperature between about -25° C. and 150° C. in the presence or absence of an inert solvent.
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