- A convenient method for the synthesis of β,γ-unsaturated sulfones through zinc-mediated C-S coupling reaction
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Through zinc-mediated coupling reaction of allylic bromides with alkane- or arenesulfonyl chlorides, β,γ-unsaturated sulfones were obtained with moderate to good yields.
- Sun, Peipei,Wang, Lei,Zhang, Yongmin
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- A new attachment/cleavage strategy: Polymer-bound allylic sulfones in a solid-phase route to trisubstituted olefins
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By tethering allyl sulfone to polystyrene (3-steps from polystyrene beads consisting of lithiation, sulfination, and allylation), trisubstituted olefins can be generated by Cα-sulfone alkylation and subsequent resin cleavage by S(N)2' nucleophilic displacement of sulfinate.
- Halm, Chris,Evarts, Jerry,Kurth, Mark J.
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- Organic oxidations promoted in vortex driven thin films under continuous flow
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With increasing concerns for the environmental impact of chemical manufacturing, reagents and processes that align with the principles of green chemistry are essential. The fundamental oxidation of organic substrates is no exception and in this report three distinct modes of green oxidation are demonstrated in a vortex fluidic device (VFD) under continuous flow: aerobic oxidation, oxidation using chlorine bleach, and oxidation using hydrogen peroxide. The VFD, which is a thin film microfluidic platform, revealed clear advantages in these oxidations in comparison to traditional batch reactor processing: Efficient mass transfer of gases in the dynamic thin film increased the rate of aerobic oxidations, and the intense micromixing allowed multi-phase oxidations to proceed efficiently, obviating the need for organic solvents and phase transfer catalysts. In addition, the rapid dissipation of heat in the VFD also improved the safety profile and stereoselectivity for exothermic oxidations.
- Pye, Scott J.,Dalgarno, Scott J.,Chalker, Justin M.,Raston, Colin L.
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- Design, Multigram Synthesis, and in Vitro and in Vivo Evaluation of Propylamycin: A Semisynthetic 4,5-Deoxystreptamine Class Aminoglycoside for the Treatment of Drug-Resistant Enterobacteriaceae and Other Gram-Negative Pathogens
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Infectious diseases due to multidrug-resistant pathogens, particularly carbapenem-resistant Enterobacteriaceae (CREs), present a major and growing threat to human health and society, providing an urgent need for the development of improved potent antibiotics for their treatment. We describe the design and development of a new class of aminoglycoside antibiotics culminating in the discovery of propylamycin. Propylamycin is a 4′-deoxy-4′-alkyl paromomycin whose alkyl substituent conveys excellent activity against a broad spectrum of ESKAPE pathogens and other Gram-negative infections, including CREs, in the presence of numerous common resistance determinants, be they aminoglycoside modifying enzymes or rRNA methyl transferases. Importantly, propylamycin is demonstrated not to be susceptible to the action of the ArmA resistance determinant whose presence severely compromises the action of plazomicin and all other 4,6-disubstituted 2-deoxystreptamine aminoglycosides. The lack of susceptibility to ArmA, which is frequently encoded on the same plasmid as carbapenemase genes, ensures that propylamycin will not suffer from problems of cross-resistance when used in combination with carbapenems. Cell-free translation assays, quantitative ribosome footprinting, and X-ray crystallography support a model in which propylamycin functions by interference with bacterial protein synthesis. Cell-free translation assays with humanized bacterial ribosomes were used to optimize the selectivity of propylamycin, resulting in reduced ototoxicity in guinea pigs. In mouse thigh and septicemia models of Escherichia coli, propylamycin shows excellent efficacy, which is better than paromomycin. Overall, a simple novel deoxy alkyl modification of a readily available aminoglycoside antibiotic increases the inherent antibacterial activity, effectively combats multiple mechanisms of aminoglycoside resistance, and minimizes one of the major side effects of aminoglycoside therapy.
- Matsushita, Takahiko,Sati, Girish C.,Kondasinghe, Nuwan,Pirrone, Michael G.,Kato, Takayuki,Waduge, Prabuddha,Kumar, Harshitha Santhosh,Sanchon, Adrian Cortes,Dobosz-Bartoszek, Malgorzata,Shcherbakov, Dimitri,Juhas, Mario,Hobbie, Sven N.,Schrepfer, Thomas,Chow, Christine S.,Polikanov, Yury S.,Schacht, Jochen,Vasella, Andrea,B?ttger, Erik C.,Crich, David
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- Highly porous conjugated polymers for selective oxidation of organic sulfides under visible light
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High surface area porous conjugated polymers were synthesized via the high internal phase emulsion polymerization technique and micropore engineering as efficient heterogeneous photocatalysts for highly selective oxidation of organic sulfides to sulfoxides under visible light. This journal is the Partner Organisations 2014.
- Wang, Zi Jun,Ghasimi, Saman,Landfester, Katharina,Zhang, Kai A. I.
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- Polyvinylpolypyrrolidone-supported boron trifluoride (PVPP-BF3): Highly efficient catalyst for chemoselective oxygenation of sulfides to sulfones by H2O2
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A highly efficient method for the oxidation of sulfides to sulfones using polyvinylpolypyrrolidone-supported boron trifluoride (PVPP-BF3) in the presence of (35%) hydrogen peroxide has been developed. This procedure cleanly oxidizes dialkyl and alkyl aryl sulfides to the corresponding sulfones in excellent yields at room temperature.
- Mokhtary, Masoud,Lakouraj, Moslem Mansour,Niaki, Masoumeh Rastegar
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- Oxidation of sulfides including DBT using a new vanadyl complex of a non-innocent o-aminophenol benzoxazole based ligand
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Reaction of a non-innocent o-aminophenol benzoxazole based ligand HLBAP with VOCl3 afforded a vanadyl complex, VOLBIS (SQ), in which SQ is a 2,4-di-tert-butylsemiquinone produced from hydrolysis of HLBAP. The crystal structure of VOLBIS (SQ) exhibits an octahedral geometry with the VO2+ center coordinated by two nitrogen and one oxygen atoms of LBAP and two oxygen atoms of SQ. Electrochemical studies showed quasi-reversible metal-centered reduction and ligand-centered oxidation of complex. The magnetic moment of VOLBIS (SQ) is consistent with the spin-only value expected for S?=?1/2 system. The neutral species of VOLBIS (SQ) is EPR active, which is consistent with a paramagnetic electronic ground state (S?=?1/2). This result is in accordance with the vanadyl (IV) moiety surrounded by tridentate iminobenzosemiquinonate anion radical (HLBIS)?- and benzosemiquinone ligand (SQ)?. The theoretical calculations confirm the experimental results. Furthermore, we present the optimal conditions for maximum efficiency of sulfide oxidation for oxidative desulfurization with hydrogen peroxide and 6 times reusability of catalyst for sulfoxidation of dibenzothiophene.
- Saeedi, Roonak,Safaei, Elham,Lee, Yong-Ill,Lu?nik, Janez
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- Indium-mediated Coupling Reaction of Sulfonyl Chlorides with Alkyl Bromides in Water. A Facile Synthesis of Sulfones
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Indium-mediated coupling of alkyl bromides with aromatic sulfonyl chlorides gives the corresponding sulfones in aqueous media with moderate to good yields.
- Wang, Lei,Zhang, Yongmin
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- A convenient synthesis of sulfones using zinc mediated coupling reaction of sulfonyl chlorides with alkyl halides in aqueous media
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An efficient procedure for the preparation of sulfones has been developed through a simple reaction of aromatic sulfonyl chlorides with suitable alkyl halides mediated by commercial zinc powder in aqueous media at 0 °C ~ room temperature.
- Sun, Xinghua,Wang, Lei,Zhang, Yongmin
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- Silver-catalyzed decarboxylative radical allylation of α,α-difluoroarylacetic acids for the construction of CF2-allyl bonds
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An efficient silver-catalyzed method of decarboxylative radical allylation of α,α-difluoroarylacetic acids to build CF2-allyl bonds has been developed. Using allylsulfone as an allyl donor, α,α-difluorine substituted arylacetic acids bearing various functional groups are successfully allylated to access a series of 3-(α,α-difluorobenzyl)-1-propylene compounds in moderate to excellent yields in aqueous CH3CN solution under the mild conditions. Experimental studies disclosed that the α-fluorine substitution of arylacetic acid has a great influence on free radical activity and reactivity.
- Wang, Pingyang,Du, Pengcheng,Sun, Qianqian,Zhang, Jianhua,Deng, Hongmei,Jiang, Haizhen
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supporting information
p. 2023 - 2029
(2021/03/16)
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- A sustainable approach towards solventless organic oxidations catalyzed by polymer immobilized Nb(V)-peroxido compounds with H2O2 as oxidant
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New heterogeneous catalysts comprising of peroxidoniobium(V) complexes immobilized on amino acid grafted cross-linked poly(styrene-divinylbenzene) resin has been developed. Results of FTIR, Raman, NMR, XPS, XRD, EDX, SEM, BET, TGA, and elemental analysis confirmed the successful anchoring of triperoxidoniobium(V), [Nb(O2)3]? species to the host polymer via the pendant amino acid groups. The supported catalysts exhibited excellent performance in epoxidation of styrene and a range of cyclic and terpenic compounds under environmentally acceptable solvent-free condition, with aqueous H2O2 as oxidant. The catalytic protocols provided excellent conversion to the desired epoxide (up to 100%) with selectivity > 99%, TON as high as 1000, and high H2O2 utilization efficiency (92–97%). Moreover, the catalysts efficiently facilitated chemoselective solvent-free oxidation of a variety of thioethers to sulfones at room temperature. Simple operational strategy, easy recyclability for multiple reaction cycles with the consistent activity-selectivity profile are the additional significant attributes of the developed catalytic processes.
- Ahmed, Kabirun,Gogoi, Sandhya Rani,Islam, Nashreen S.,Saikia, Gangutri,Sultana, Sazida Yasmin,Talukdar, Hiya
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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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- COMPOSITES, METHODS AND USES THEREOF
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The present invention relates, in general terms, to methods of catalysing a reaction, including the steps of contacting a chemical entity comprising a sulphide moiety with a composite and an oxidant. The composite acts as a heterogeneous catalyst to oxidise the sulphide moiety. The present invention also relates to composites, methods of synthesising the composites and its use as a catalyst thereof.
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Page/Page column 22-23
(2021/06/04)
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- Polyoxometalate-Based Organic-Inorganic Hybrids as Heterogeneous Catalysts for Cycloaddition of CO2with Epoxides and Oxidative Desulfurization Reactions
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Self-assembly of polyoxometalates, transition metal salts, and 2,6-bis(2′-pyridyl)-4-hydroxypyridine (LOH) obtained four organic-inorganic hybrids [Co2.5(LOH)(LO)2(H2O)2(PW12O39)]·3CH3CN·2OH (1), [Zn1.5(LOH)3]·(PMo12O40)·CH3OH·2H2O (2), [Cd1.5(LOH)3]·(PW12O40)·2CH3OH·1.5H2O (3), and [Mn(LOH)2]·(PW12O40)·2CH3CN·H3O (4). Hybrid 1 exhibits an extended chain, which could be further connected into a 3D supramolecular architecture by H-bonds. Hybrids 2-4 feature monomolecular structures, which are further bridged via H-bonds to yield charming 3D supramolecular structures. Noteworthy, 1 and 2 can be employed as recyclable and highly efficient heterogeneous catalysts. The activated 1 displays a high catalytic activity for the cycloaddition reaction of CO2 and epoxides. Hybrid 2 exhibits an excellent catalytic performance for the oxidative desulfurization reaction.
- Zhao, Yu-Qing,Liu, Ying-Ying,Ma, Jian-Fang
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p. 1019 - 1027
(2021/01/13)
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- Assembly of polyoxometalate-thiacalix[4]arene-based inorganic-organic hybrids as efficient catalytic oxidation desulfurization catalysts
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Self-assembly of polyoxometalates, Ni(ii)/Ag(i) cations and tetra-[5-(mercapto)-1-methyltetrazole]-thiacalix[4]arene (L) yielded three inorganic-organic hybrids, namely, [Ni3L2(CH3OH)6(H2O)4][PMo12O40]2·3CH3OH·2H2O (1), [Ni3L2(CH3OH)6(H2O)4][PW12O40]2·3CH3OH·2H2O (2) and [Ag3L(PMo12O40)] (3). In hybrids (1) and (2), Ni(ii) cations are linked by L ligands to produce layered frameworks, and H bonds among the [PMo12O40]3?/[PW12O40]3?anions and L ligands lengthen the structures to form 3D supramolecular architectures. Hybrid (3) exhibits a 3D architecture, of which Ag(i) cations not only coordinated with the N and O atoms of L ligands and [PMo12O40]3?anions simultaneously, but also connected each other by Ag-Ag interactions. It is worth mentioning that1and3as recyclable catalysts show excellent heterogeneous catalytic activity in oxidation desulfurization reactions.
- Li, Jie,Du, Peng,Liu, Ying-Ying,Ma, Jian-Fang
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supporting information
p. 1349 - 1356
(2021/02/09)
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- Isomerisation of Vinyl Sulfones for the Stereoselective Synthesis of Vinyl Azides
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Reported is the construction, and facile base-mediated conversation of ten differently substituted 3-azido E-vinyl sulfones (γ-azido-α,β-unsaturated sulfones) into their isomeric vinyl azide counterparts. The requisite 3-azido E-vinyl sulfones were prepared from 3-bromo E-vinyl sulfones, which in turn were accessed from allyl sulfones via a bromination-elimination sequence. In relation to this a one-pot azidation-isomerisation sequence was developed which enabled the direct formation of the vinyl azides from the corresponding 3-bromo E-vinyl sulfones. Similarly, a convenient one-pot Horner–Wadsworth–Emmons olefination-isomerisation approach was utilised in order to prepare some of the allylic sulfones used in this study. The vinyl azide forming process typically proceeded with high levels of Z-selectivity, although this was dependent on the vinyl sulfone substitution pattern. Thus, with either no substituent or a methyl group in the γ- or β-position, relative to the sulfone, good, to high levels of Z-selectivity (Z/E = 85:15 to ≥ 95:5) were obtained. However, incorporation of an α-sulfonyl methyl substituent led to an E-selective process (Z/E = 20:80). A non-bonding interaction between the azido group and the α-sulfonyl vinylic proton is proposed, which acts as a conformational control mechanism to help guide the stereochemical outcome.
- Collins, Niall,Connon, Robert,Evans, Paul,Sánchez-Sanz, Goar
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supporting information
p. 6228 - 6235
(2020/10/02)
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- A General Photocatalytic Route to Prenylation
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Prenylation is an essential reaction on which nature relies to modify properties of molecules and build terpenoids, but remains a challenging chemical reaction. Aiming to capitalize on recent advances in photocatalysis to easily and cleanly generate a broad range of carbon based radicals, we have developed a prenyl transfer reagent that is captured by transiently generated radicals. The reagent can be made in bulk, is bench stable, and broadly applicable such that it can be used with existing photocatalytic methods with very few changes to reaction conditions. Ultimately, this provides a true drop-in solution for prenylation, expanding the scope of substrates that can be readily prenylated.
- Rathnayake, Manjula D.,Weaver, Jimmie D.
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supporting information
p. 1433 - 1438
(2019/06/13)
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- Cobalt Single-Atom-Intercalated Molybdenum Disulfide for Sulfide Oxidation with Exceptional Chemoselectivity
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The identification of chemoselective oxidation process en route to fine chemicals and specialty chemicals is a long-standing pursuit in chemical synthesis. A vertically structured, cobalt single atom-intercalated molybdenum disulfide catalyst (Co1-in-MoS2) is developed for the chemoselective transformation of sulfides to sulfone derivatives. The single-atom encapsulation alters the electron structure of catalyst owing to confinement effect and strong metal–substrate interaction, thus enhancing adsorption of sulfides and chemoselective oxidation at the edge sites of MoS2 to achieve excellent yields of up to 99% for 34 examples. The synthetic scopes can be extended to sulfide-bearing alkenes, alkynes, aldehydes, ketones, boronic esters, and amines derivatives as a toolbox for the synthesis of high-value, multifunctional sulfones and late-stage functionalization of pharmaceuticals, e.g., Tamiflu. The synthetic utility of cobalt single atom-intercalated MoS2, together with its reusability, scalability, and simplified purification process, renders it promising for industrial productions.
- Chen, Zhongxin,Liu, Cuibo,Liu, Jia,Li, Jing,Xi, Shibo,Chi, Xiao,Xu, Haisen,Park, In-Hyeok,Peng, Xinwen,Li, Xing,Yu, Wei,Liu, Xiaowang,Zhong, Linxin,Leng, Kai,Huang, Wei,Koh, Ming Joo,Loh, Kian Ping
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- A biradical oxo-molybdenum complex containing semiquinone and: o -aminophenol benzoxazole-based ligands
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We report a new mononuclear molybdenum(iv) complex, MoOLBISLSQ, in which LSQ (2,4-di-tert-butyl o-semibenzoquinone ligand) has been prepared from the reaction of the o-iminosemibenzoquinone form of a tridentate non-innocent benzoxazole ligand, LBIS, and MoO2(acac)2. The complex was characterized by X-ray crystallography, elemental analysis, IR and UV-vis spectroscopy and magnetic susceptibility measurements. The crystal structure of MoOLBISLSQ revealed a distorted octahedral geometry around the metal centre, surrounded by one O and two N atoms of LBIS and two O atoms of LSQ. The effective magnetic moment (μeff) of MoOLBISLSQ decreased from 2.36 to 0.2 μB in the temperature range of 290 to 2 K, indicating a singlet ground state caused by antiferromagnetic coupling between the metal and ligand centred unpaired electrons. Also, the latter led to the EPR silence of the complex. Cyclic voltammetry (CV) studies indicate both ligand and metal-centered redox processes. MoOLBISLSQ was applied as a catalyst for the oxidative cleavage of cyclohexene to adipic acid and selective oxidation of sulfides to sulfones with aqueous hydrogen peroxide. This journal is
- Galindo, Agustín,Jagli?i?, Zvonko,Masoumpour, Marzieh Sadat,Nasibipour, Mina,Safaei, Elham,Wojtczak, Andrzej
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p. 40853 - 40866
(2020/11/23)
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- Two polyoxometalate-based inorganic-organic hybrids and one coordination polymer assembled with a functionalized calix[4]arene: Catalytic and electrochemical properties
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Self-assembly of 4-pyridyl-functionalized calix[4]arene ligand 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,26,27,28-tetrakis[(4-pyridylmethyl)oxy]calix[4]arene (L), Ag(I)/Cd(II) cations and polyoxometalate obtained two inorganic-organic hybrids [Ag3(L)2][PMo12O40]·CH3CN·4H2O (1), [Ag3(L)2][PMo12O40]·2DMA·0.5EtOH (2) and one complex [Cd3(L)2Cl6]·4CH3CN·4H2O (3) (DMA = N,N-dimethylacetamide). Hybrids 1 and 2 have fascinating one-dimensional chains, which are linked by hydrogen bonds between the C atoms of L ligands and the O atoms of [PMo12O40]3? anions to generate supramolecular layers. 3 displays a thick layer containing trinuclear Cd(II) clusters. Noteworthy, hybrid 1 exhibits excellent heterogeneous catalytic activity for oxidative desulfurization reaction and obvious electrocatalytic activity for oxidize ascorbic acid and reduce NaBrO3. Complex 3 shows heterogeneous catalytic ability for Knoevenagel condensation reaction.
- Li, Zhuo,Liu, Ying-Ying,Xu, Guo-Hai,Ma, Jian-Fang
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- Efficient Catalytic Oxidative Desulfurization toward Thioether and Sulfur Mustard Stimulant by Polyoxomolybdate-Resorcin[4]arene-Based Metal-Organic Materials
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The design and synthesis of effective and recyclable oxidative desulfurization catalysts is of great importance in view of environmental protection and human health. Herein, a family of polyoxomolybdate-based inorganic-organic hybrid materials, namely, [Mn(TMR4A)(H2O)4][Mo6O19]·0.5CH3CH2OH·H2O (1), [Ni(TMR4A)(H2O)4][Mo6O19]·0.5CH3CH2OH·H2O (2), [Zn(TMR4A)(H2O)4][Mo6O19]·0.5CH3CH2OH·H2O (3), and [Co2(TMR4A)2(H2O)4(β-Mo8O26)]·CH3CN·12H2O (4), were assembled by the functionalized resorcin[4]arene ligand (TMR4A) with polyoxomolybdate and metal ions under solvothermal conditions. In isostructural 1-3, the [M(TMR4A)(H2O)4]2+ species (M = MnII, NiII, ZnII) and [Mo6O19]2- anions are held together via C-H···O hydrogen bonds to give a 3D supramolecular architecture. In 4, two [Co(TMR4A)(H2O)2]2+ cations were linked by one [β-Mo8O26]4- anion to produce an attractive molecular dimer. Remarkably, 1-4, as recyclable heterogeneous catalysts, exhibit efficient catalytic oxidation desulfurization activities toward thioethers. Particularly, 1, as a representative example, features selective catalytic oxidation for sulfur mustard simulant. Moreover, their electrochemical properties were also studied.
- Guo, Ting-Ting,Ma, Jian-Fang,Yang, Jin,Yu, Ming-Yue
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supporting information
(2020/04/02)
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- Cyanide-Mediated Synthesis of Sulfones and Sulfonamides from Vinyl Sulfones
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We report a facile synthesis of sulfones, β-keto sulfones, and sulfonamides from vinyl sulfones via an addition-elimination sequence where in situ generation of nucleophilic sulfinate ion is mediated by cyanide. The use vinyl sulfones renders high selectivity for S -alkylation to produce sulfones in high yields. In the presence of N -bromosuccinimide, primary and secondary amines underwent sulfonamide formation. A preliminary mechanistic study showed the formation of acrylonitrile as an innocent byproduct, without interfering with the desired reaction pathway while generating a sulfinate nucleophile.
- Lee, Ji-Woong,Roy, Tamal
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p. 455 - 458
(2020/03/13)
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- Synthesis of 4,4-Difluoroalkenes by Coupling of α-Substituted α,α-Difluoromethyl Halides with Allyl Sulfones under Photoredox Catalyzed Conditions
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Photoredox-catalyzed allylation of α-gem-difluorinated organohalides with allyl sulfones proceeded smoothly under visible light irradiation to give 4,4-difluoroalkenes in good yields. In the presence of catalytic Ru(bpy)3Cl2, Hantzsch ester, and diisopropylethylamine, the reaction was complete within 2 h. Using the same methodology, three-component cascade reactions to give 6,6-difluoroalkenes were carried out successfully.
- Uno, Misae,Sumino, Shuhei,Fukuyama, Takahide,Matsuura, Makoto,Kuroki, Yoshichika,Kishikawa, Yosuke,Ryu, Ilhyong
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p. 9330 - 9338
(2019/08/12)
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- A practical synthesis of functionalized isoindolinones via [3?+?3] benzannulation of 1,3-bissulfonylpropenes and 4-arylmethylene-2,3-dioxopyrrolidines
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A straightforward synthesis of isoindolinones has been developed via a [3 + 3] benzannulation of 4-arylmethylene-2,3-dioxopyrrolidines and 1,3-bissulfonylpropenes (or 4-sulfonylcrotonates). A series of functionalized isoindolinones were obtained in excellent yields. The reaction could be carried out under mild conditions without transition metal catalyst. The finding provides a practical approach for the preparation of isoindolinone derivatives with potential biological activities.
- Tang, Xiang-zheng,zhou, Jing-xuan,Liang, Hua-ju,Zhang, Xue-jing,Yan, Ming,Chan, Albert S.C.
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supporting information
p. 147 - 149
(2018/12/11)
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- Water-soluble polymer anchored peroxotitanates as environmentally clean and recyclable catalysts for mild and selective oxidation of sulfides with H2O2 in water
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Anchoring of peroxotitanium (pTi) species to linear water-soluble acrylic acid based polymers, poly(sodium acrylate) (PA) and poly(sodium methacrylate) (PMA) led to the successful synthesis of a pair of new, water-tolerant and recyclable catalysts of the type [Ti2(O2)2O2(OH)2]4-—L (L = PA or PMA), highly effective in chemoselective sulfoxidation of organic sulfides with 30% H2O2 in aqueous medium at ambient temperature. The catalytic protocol is high yielding (TOF up to 11,280 h?1), operationally simple as well as environmentally clean and safe, being free from halide, or any other toxic auxiliaries. The catalysts are sufficiently stable to afford easy recyclability for at least 10 consecutive reaction cycles of sulfoxidation with consistent activity selectivity profile. Oxidation of dibenzothiophene (DBT) to respective high purity sulfoxide or sulfone could also be accomplished using the same catalysts by variation of reaction conditions.
- Ahmed, Kabirun,Saikia, Gangutri,Paul, Sivangi,Baruah, Satyajit Dey,Talukdar, Hiya,Sharma, Mitu,Islam, Nashreen S.
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- Fe3O4?BNPs?SiO2-SO3H as a highly chemoselective heterogeneous magnetic nanocatalyst for the oxidation of sulfides to sulfoxides or sulfones
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To achieve green chemistry goals and also to reduce the cost of catalysts as well as to avoid producing toxic wastes and show the importance of separation and recycling of catalysts from the reaction medium, in this work, we describe the preparation and characterization of magnetic acidic boehmite nanoparticles as a heterogeneous catalyst, which is called Fe3O4?BNPs?SiO2-SO3H. This catalyst works efficiently in the selective oxidation of sulfides to sulfoxides or sulfones in the presence of H2O2 as a green oxidant. It can easily be separated from the reaction medium by using an external magnet and it was recycled 6 times without loss of magnetic catalytic properties.
- Ghanbari Kermanshahi, Mohammad,Bahrami, Kiumars
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p. 36103 - 36112
(2019/11/20)
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- SO2 conversion to sulfones: Development and mechanistic insights of a sulfonylative Hiyama cross-coupling
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A Pd-catalyzed Hiyama cross-coupling reaction using SO2 is described. The use of silicon-based nucleophiles leads to the formation of allyl sulfones under mild conditions with a broad functional group tolerance. Control experiments coupled with DFT calculations shed light on the key steps of the reaction mechanism, revealing the crucial role of a transient sulfinate anion.
- Adenot, Aurélien,Char, Jo?lle,Von Wolff, Niklas,Lefèvre, Guillaume,Anthore-Dalion, Lucile,Cantat, Thibault
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supporting information
p. 12924 - 12927
(2019/11/05)
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- Highly stable polyoxometalate-resorcin[4]arene-based inorganic-organic complexes for catalytic oxidation desulfurization
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Self-assembly of a resorcin[4]arene-based ligand (TMR4A) with metal salts and H3PMo12O40·xH2O offers two isostructural complexes, namely, [Ni2Cl(TMR4A)2(CH3CN)2]·[PMo12O40]·4CH3CN (1) and [Co2Cl(TMR4A)2(CH3CN)2]·[PMo12O40]·4CH3CN (2). In both 1 and 2, one Cl? anion bridges two metal cations, and each metal cation is further chelated by four 2-mercaptopyridine N-oxide groups of one TMR4A, producing a [M2Cl(TMR4A)2]3+ dimer (M?=?Ni or Co). The negative [PMo12O40]3? as a counter-anion balances the positive charge. Markedly, 1 and 2 exhibit high stability in aqueous solutions with different pH values and in organic solvents. Remarkably, the efficient heterogeneous catalytic capability for oxidative desulfurization was studied by suing 1 and 2 as recycled catalysts. Moreover, the electrochemical behaviors of the two compounds were discussed as well.
- Yu, Ming-Yue,Yang, Jin,Xu, Xianxiu,Ma, Jian-Fang,Wang, Zhenxing
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- Polyoxometalate-Bridged Cu(I)- And Ag(I)-Thiacalix[4]arene Dimers for Heterogeneous Catalytic Oxidative Desulfurization and Azide-Alkyne "click" Reaction
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Two remarkable polyoxometalate-bridged Cu(I)- and Ag(I)-thiacalix[4]arene dimers, namely, [Cu4(SiW12O40)(L)2(DMF)2]·2EtOH·DMF (1-Cu) and [Ag4(PMo12O40)(L)2]·OH (1-Ag), were prepared by using a new thiacalix[4]arene, metal cation and polyoxometalate (L = tetra[2-(ethylthio)-1-methyl-1H-imidazole]-thiacalix[4]arene). In 1-Cu and 1-Ag, two thiacalix[4]arenes were linked together by one [SiW12O40]4- or [PMo12O40]3- anion via two metal cations to give a molecular dimer. Further, adjacent dimers were extended into a high-dimensional supramolecular architecture through hydrogen bonds. Markedly, these molecular dimers are exceedingly stable in organic solvents and then were employed as efficient catalysts for catalytic oxidation desulfurization as well as the azide-alkyne "click" reaction.
- Yu, Ming-Yue,Guo, Ting-Ting,Shi, Xiao-Chuan,Yang, Jin,Xu, Xianxiu,Ma, Jian-Fang,Yu, Zhen-Tao
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p. 11010 - 11019
(2019/08/26)
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- Facile synthesis of substituted diaryl sulfones: Via a [3 + 3] benzannulation strategy
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A base-mediated [3 + 3] benzannulation strategy for the conversion of 1,3-bis(sulfonyl)propenes and β,γ-unsaturated α-ketoesters to diaryl sulfones has been developed. This method provides facile, metal-free and efficient access to highly substituted diaryl sulfones in good to excellent yields. In addition, the sulfonyl group could be easily removed or converted to other functional groups via an organostannane intermediate.
- Tang, Xiang-Zheng,Tong, Lang,Liang, Hua-Ju,Liang, Jie,Zou, Yong,Zhang, Xue-Jing,Yan, Ming,Chan, Albert S. C.
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supporting information
p. 3560 - 3563
(2018/05/26)
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- Fe3O4/PEG-SO3H as a heterogeneous and magnetically-recyclable nanocatalyst for the oxidation of sulfides to sulfones or sulfoxides
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We present below a sulfonated-polyethylene glycol-coated Fe3O4 nanocomposite (Fe3O4/PEG-SO3H) as a greatly effective and ecological nanocatalyst for the selective oxidation of sulfides to sulfoxides or sulfones with brilliant yields under solvent-free conditions by employing 30% hydrogen peroxide as the oxidant. A number of sulfides containing alcohol, ester, and aldehyde functional groups were fruitfully and selectively oxidized without altering the desired characteristics. The magnetic nanocatalyst (Fe3O4/PEG-SO3H) can be conveniently and swiftly retrieved through the utilization of an external magnetic tool and recycled for more than 10 reaction runs without significantly decreasing its catalytic behavior.
- Mirfakhraei, Saeideh,Hekmati, Malak,Eshbala, Fereshteh Hosseini,Veisi, Hojat
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p. 1757 - 1761
(2018/02/09)
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- Oxygenation of sulfides catalysed by SBA-15-immobilized molybdenum(VI) complex of a bis(phenol) diamine ligand using aqueous hydrogen peroxide as a green oxidant
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A highly efficient and reusable molybdenum-based catalyst has been synthesized by covalent grafting of a bis(phenol) diamine ligand, namely 2-(((2-bromoethyl)(2-((3,5-di-tert-butyl-2-hydroxybenzyl)amino)ethyl)amino)methyl)-4,6-di-tert-butylphenol, onto functionalized ordered mesoporous silica (SBA-15) followed by complexation with MoO2(acac)2. The resulting organic–inorganic hybrid material was found to be a highly effective catalyst for oxygenation of various sulfides to their corresponding sulfoxides or sulfones. The catalyst was characterized using transmission and scanning electron microscopies, X-ray photoelectron, Fourier transform infrared and atomic absorption spectroscopies, Brunauer–Emmett–Teller surface area analysis and thermogravimetric analysis. Mild reaction conditions, high selectivity and easy recovery and reusability of the catalyst render the presented protocol very useful for addressing industrial needs and environmental concerns.
- Saberikia, Iraj,Safaei, Elham,Karimi, Babak,Lee, Yong-Iii
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- MANUFACTURING METHOD OF COMPOUND HAVING SULFONYL GROUP
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The present invention relates to a method for manufacturing a compound having a sulfonyl group, which includes a step for reacting thiosulfonates in a solvent comprising nucleophilic bases with an electrophilic agent. Accordingly, the present invention can manufacture the compound having the sulfonyl group with a variety of structures with high efficiency and high yield through more simplified processes than conventional methods.COPYRIGHT KIPO 2018
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Paragraph 0108; 0109; 0121-0124
(2018/10/03)
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- A highly efficient reusable homogeneous copper catalyst for the selective aerobic oxygenation sulfides to sulfoxides
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Readily available copper showed efficient activity and great selectivity for the homogeneous catalysis of oxidation of sulfides to sulfoxides using molecular oxygen as the oxidant. The reaction proceeds under mild conditions in the presence of a catalytic amount of TEMPO. Importantly, the catalysts could be conveniently recovered and reused. And this methodology was proved to be applicable for the transformation of various aromatic and aliphatic sulfides into the corresponding sulfoxides with high conversion and high selectivity.
- Ren, Cheng,Fang, Runxing,Yu, Xiaochun,Wang, Shun
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supporting information
p. 982 - 986
(2018/02/13)
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- Synthesis of new oxido-vanadium complexes: Catalytic properties and cytotoxicity
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Reaction of 2,3-dihydroxy benzaldehyde with 2-({2-amino phenyl}diazenyl)phenol afforded the ligand 3-(2-(2-hydroxyphenyl)diazenyl)- 4-alkylphenyliminomethyl)benzene-1,2-diol. Reaction of H2L with VOSO4. 5H2O gave the oxido-vanadium(IV) complexes [(L)VO], which exhibited a quasi-reversible oxidative cyclic voltammetric response in a V(IV)/V(V) oxidative process. The complexes act as catalysts in the oxidation of organic thioethers and bromination of phenol. Their cytotoxic properties were examined for three cancer cell lines.
- Das, Uttam,Pattanayak, Poulami,Santra, Manas Kumar,Chattopadhyay, Surajit
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- Synthesis, characterization, spectral and catalytic activity of tetradentate (NNNO) azo-imine Schiff base copper(II) complexes
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The hexadentate ligand, 2,2′-bis(salicylideneamino)azobenzene, 1 has been synthesized from 2,2′-diaminoazobenzene and salicylaldehyde in refluxing diethyl ether. Reaction of ligand 1 with Cu(II) acetate and Cu(II) perchlorate separately in methanol afforded tetradentate (N,N,N,O) Cu(II) complexes, Cu(L) & [Cu(HL)]ClO4 respectively [where H2L represent the one imine moiety cleavage product of ligand 1 (H represents the dissociable amino and phenolic protons)]. These were characterized by microanalytical data and spectroscopic studies. In addition, the crystal structures of the ligand 1 and complexes Cu(L) & [Cu(HL)]ClO4 were determined by X-ray diffraction analysis. The diffraction analysis revealed that the ligand (H2L) binds Cu(II) centers in (N,N,N,O) tetra dentate fashion in distorted square planer geometry. In complex [Cu(HL)]ClO4 the apical position of copper center is weakly coordinated with one perchlorate ion. The dimeric structure of the molecule [Cu(HL)]ClO4 is stabilized through NH2···O hydrogen bonds. The fluorescence and redox property of ligand 1 and complexes Cu(L) & [Cu(HL)]ClO4 were studied. Preliminary DFT calculations were carried out using crystallographic coordinates to understand the electronic spectra and redox properties of the ligand and complexes. The complex Cu(L) shows very good catalytic activities towards oxidation of benzyl alcohol to benzaldeyhde (under solvent-free condition) and organic thioethers to sulfoxide and sulfones using H2O2 as the oxidant.
- Pratihar, Jahar Lal,Mandal, Paritosh,Brand?o, Paula,Mal, Dasarath,Felix, Vitor
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p. 221 - 228
(2018/05/22)
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- Direct N-H/α,α,β,β-C(sp3)-H functionalization of piperidine via an azomethine ylide route: synthesis of spirooxindoles bearing 3-substituted oxindoles
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A protocol for the direct functionalization of N-H/α,α,β,β-C(sp3)-H of piperidine without any metal or external oxidants is reported. This reaction is promoted by 4-(trifluoromethyl)benzoic acid via an azomethine ylide intermediate. This is a simple method for the synthesis of spirooxindoles bearing 3-substituted oxindole moieties.
- Du, Yanlong,Yu, Aimin,Jia, Jiru,Zhang, Youquan,Meng, Xiangtai
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supporting information
p. 1684 - 1687
(2017/02/10)
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- Efficient synthesis of aliphatic sulfones by Mg mediated coupling reactions of sulfonyl chlorides and aliphatic halides
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Sulfonyl chlorides were reduced to anhydrous sulfinate salts with magnesium under sonication. These sulfinates were alkylated to sulfones with alkyl chlorides in the presence of catalytic sodium iodide under sonication. A variety of aliphatic sulfones was efficiently prepared by this one-pot two-step procedure.
- Fu, Ying,Xu, Qin-Shan,Li, Quan-Zhou,Du, Zhengyin,Wang, Ke-Hu,Huang, Danfeng,Hu, Yulai
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supporting information
p. 2841 - 2845
(2017/04/03)
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- Green Organocatalytic Oxidation of Sulfides to Sulfoxides and Sulfones
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A highly efficient synthetic methodology towards the selective synthesis of sulfoxides and sulfones is reported using a cheap and green organocatalytic method. Starting from sulfides and using 2,2,2-trifluoroacetophenone as the organocatalyst and H2O2 as the oxidant, the high-yielding preparation of sulfoxides or sulfones is described, being dependent on the reaction conditions.
- Voutyritsa, Errika,Triandafillidi, Ierasia,Kokotos, Christoforos G.
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p. 917 - 924
(2017/02/15)
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- Catalyst-free oxidation of sulfides to sulfoxides and diethylamine catalyzed oxidation of sulfides to sulfones using Oxone as an oxidant
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Abstract: We describe here our journey from the failure of our attempts in controlled oxidation of sulfides to sulfoxides using an Oxone–KBr combination to our success in the development of a catalyst-free protocol for the oxidation of sulfides to sulfoxides using Oxone as an oxidant. We also describe the failure of our attempts at the oxidation of sulfides to sulfones using an excess of Oxone–KBr as well as Oxone, and our success towards the development of a rapid, scalable and chromatography-free protocol for the oxidation of sulfides to sulfones using diethylamine–Oxone as an unprecedented catalyst–oxidant combination.
- Kupwade,Khot,Lad,Desai,Wadgaonkar
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p. 6875 - 6888
(2017/10/06)
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- Sulfone compound (by machine translation)
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[Problem] to safely and conveniently, highly selective, sulfide compound producing a sulfone compound. [Solution] pH is 9 - 12 under, water or water-insoluble solvent or an aromatic hydrocarbon-based solvent mixture, sodium hypochlorite is used as oxidizing agent, (1) (2) from the compound represented by the formula sulfide sulfone compound represented by the formula manufacturing method. (R1 And R2 Are each independently an alkyl, aryl, aralkyl, heteroaryl)[Drawing] no (by machine translation)
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Paragraph 0043
(2017/10/06)
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- 1,1,2,2-Tetrahydroperoxy-1,2-diphenylethane as new oxidant for chemoselective and catalyst free oxidation of sulfides to sulfoxides and sulfones
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A catalyst free and chemoselective oxidation of sulfides to sulfoxides or sulfones was developed using 1,1,2,2-tetrahydroperoxy-1,2-diphenylethane as a new oxidant. This scope has shown the achievement of various sulfoxides and sulfones which were obtained selectively in high yields at room temperature.
- Khosravi, Kaveh,Naserifar, Shirin,Mahmoudi, Boshra,Khalaji, Kobra
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p. 316 - 321
(2017/02/18)
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- Synthesis of Sulfones and Sulfonamides via Sulfinate Anions: Revisiting the Utility of Thiosulfonates
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Simple and high-yielding strategies for the production of a variety of sulfones and sulfonamides, using thiosulfonates synthesized by copper-catalyzed aerobic dimerization, are reported. Although thiosulfonates are an old class of compound, practical methods for their synthesis and utilization have not been rigorously developed. In this study, we revisit the reactions of easily accessible thiosulfonates to form sulfinate anions. Because of the similar reactivity of thiosulfonates and metal sulfinates derived from toxic SO2, thiosulfinates are proposed to be stable, nontoxic alternatives to metal sulfinate salts.
- Shyam, Pranab K.,Jang, Hye-Young
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p. 1761 - 1767
(2017/02/10)
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- Catalytic Activity of Crystallographically Characterized Organic–Inorganic Hybrid Containing 1,5-Di-amino-pentane Tetrachloro Manganate with Perovskite Type Structure
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Abstract: Layered 2D organic–inorganic hybrid perovskite (OIHS) of the diammonium series, 1,5 di-aminepentane tetrachloro mangenate ([NH3–(CH2)5–NH3] MnCl4) was prepared by slow evaporation and reducing temperature method and characterized by single crystal X-ray diffraction analysis. Its structure consists of organic cation, [NH3(CH2)5NH3]+2 extended in a zigzag fashion and inorganic anion, [MnCl6]?2 where Mn2+ is coordinated by six Cl? ion in octahedral fashion. The organic and inorganic segments are alternately stacked along c-axis where inorganic layer is extended through corner-shared octahedra sandwiched by the di-aminopentane molecules. The layers (organic and inorganic) were connected to each other through N–HCl hydrogen bonds and van-der Waals interaction to build cation–anion–cation cohesion. The hybrid crystal had orthorhombic non-centrosymetric system having I212121 space group with unit cell parameters a = 7.1742(3) ?, b = 7.3817(3) ?, c = 23.9650(10) ?, V = 1269.13 ?3 and Z = 4. The hybrid exhibited excellent catalytic activity towards sulphide and alkene oxidation using aqueous H2O2 as an oxidant. Graphical Abstract: OIHS of the diammonium series [NH3–(CH2)5–NH3] MnCl4; 1,5 di-aminepentane tetrachloro mangenate were prepared by slow evaporation and temperature decrease method, characterized by single crystal X-ray diffraction. This complex exhibits excellent catalytic activity towards sulphide oxidation and alkene oxidation using aqueous H2O2 as an oxidant. [Figure not available: see fulltext.].
- Mondal, Paramita,Abdel-Aal, Seham Kamal,Das, Debasis,Islam, Sk Manirul
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p. 2332 - 2339
(2017/08/22)
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- Enhanced aqueous oxidation activity and durability of simple manganese(III) salen complex axially anchored to maghemite nanoparticles
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Simple Mn-salen complex was anchored coordinatively to γ-Fe2O3 nanoparticles through amine functionality which provide a new magnetically recoverable nanocatalyst with high oxidation activity and stability. Catalyst characterization was performed using FT-IR, UV-Vis, XRD, EDS, TGA and ICP-AES. TEM image revealed a quasi-spherical structure with size smaller than 20 nm for nanocatalyst. A thermal stability up to around 300 °C was verified for prepared nanocatalyst based on thermogravimetric analysis. Finally, the catalytic performance of magnetically recoverable Mn-catalyst was exploited in the green oxidation of different types of functional groups including olefins, alcohols, saturated hydrocarbons and sulfur containing compounds with n-Bu4NHSO5 (TBAOX) in water under heterogeneous conditions. The salen catalyst proved to be reusable for at least eight times and the oxidant's by-product (n-Bu4NHSO4) could also be recycled.
- Rezaeifard, Abdolreza,Jafarpour, Maasoumeh,Farrokhi, Alireza,Parvin, Sousan,Feizpour, Fahimeh
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p. 64640 - 64650
(2016/07/21)
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- A chemoselective oxidation of sulfides to sulfoxides and sulfones using urea-2,2-dihydroperoxypropane as a novel oxidant
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Background: Sulfoxides and sulfones have been in the center of attention due to their wide range of promises in various approaches. The functional groups presented in these compounds serve as important building blocks in numerous natural, pharmeceutical and agricultural compounds. These deriatives have been prepared through a multitude of routes which were accompanied by several drawbacks. Therefore, there has been an ever-increasing interest to find a new methodology that leads to the production of these compounds via an environmentally benign path bringing about high yields. Recently, gem-dihydroperoxides have attracted much attention due to their oxidizing power and they have been utilized in several oxidation processes. Methods: We carried out a chemoselective oxidation of sulfides to sulfoxides and sulfones on treatment with urea-2,2-dihydroperoxypropane, a solid oxidant composed of equal amounts of 2,2-dihydroperoxypropane and urea, using THF as the solvent under catalyst-free conditions at room temprature. Results: Sulfides possessing a variety of substitutions namely dialkyl, diaryl, ally l and alkyl-aryl were subjected to the optimized reaction conditions and they could successfully afford different amounts of sulfoxides and sulfones depending on the amount of the oxidant utilized. Based on the results, electron-donating groups accelerated the reaction while electron-withdrawing substituents lowered the reactivity. Conclusion: Urea-2,2-dihydroperoxypropane as a solid oxidant which can be stored for several months without any loss in its activity has proved its capability to oxidize sulfides to sulfoxides and sulfones under catalyst-free and mild conditions. This approach is a cost-effective and environmentally benign methodology via which the products have been synthesized in high yields and short reaction times.
- Khosravi, Kaveh,Naserifar, Shirin,Asgari, Atefeh
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p. 749 - 756
(2017/02/05)
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- Synthesis and characterization of insoluble cobalt(II), nickel(II), zinc(II) and palladium(II) Schiff base complexes: Heterogeneous catalysts for oxidation of sulfides with hydrogen peroxide
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The condensation reaction of 1,2-bis(2'-aminophenoxy)benzene with 2-pyridinecarbaldehyde in a mole ratio of 1:2 gives a new Schiff base ligand (L). Four Schiff base complexes, CoL(NO3)2 (1), NiLCl2 (2), ZnL(NO3)2 (3) and Pd2LCl4 (4) have been prepared by direct reaction of the ligand (L) and appropriate metal salts. The Schiff base ligand (L) has been characterized by IR, 1H NMR and 13C NMR spectroscopy and elemental analysis. Also, all complexes have been characterized by IR and XRD spectroscopy techniques and elemental analysis. The synthesized complexes have very poor solubility in all polar and non-polar solvents such as: H2O, MeOH, EtOH, CH3CN, DMSO, DMF, CHCl3, CH2Cl2, THF, etc; therefore, they have been used as heterogeneous catalysts. Catalytic performance of the complexes was studied in oxidation of thioanisole using hydrogen peroxide (H2O2) as the oxidant. Various factors including the reaction temperature, amount of oxidant and catalyst amount were optimized. The palladium Schiff base complex, Pd2LCl4 (4), shows better catalytic activity than other complexes. Therefore, the Pd(II) Schiff base complex has been used as a catalyst for oxidation of different sulfides to their corresponding sulfones in acetonitrile with hydrogen peroxide as the oxidant. The palladium Schiff base complex, Pd2LCl4 (4), has shown a very good recyclability, up to five times, without any appreciable decreases in catalytic activity and selectivity.
- Menati, Saeid,Amiri Rudbari, Hadi,Askari, Banafshe,Riahi Farsani, Mostafa,Jalilian, Fariba,Dini, Ghasem
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p. 347 - 356
(2016/04/20)
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- Polyoxomolybdate-Calix[4]arene Hybrid: A Catalyst for Sulfoxidation Reactions with Hydrogen Peroxide
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An easily accessible polyoxomolybdate-calix[4]arene hybrid 1 has been synthesized and applied as a heterogeneous catalyst in the sulfoxidation of thioethers to sulfoxides and to sulfones under strictly stoichiometric amounts of 30% H2O2 in CH3CN as the solvent. This study represents the first promising example of successful employment of calixarenes-polyoxometalate (POM) hybrid materials in the area of catalytic oxidations.
- Meninno, Sara,Parrella, Alessandro,Brancatelli, Giovanna,Geremia, Silvano,Gaeta, Carmine,Talotta, Carmen,Neri, Placido,Lattanzi, Alessandra
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supporting information
p. 5100 - 5103
(2015/11/03)
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- Peroxoniobium(v)-catalyzed selective oxidation of sulfides with hydrogen peroxide in water: A sustainable approach
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An efficient and eco-compatible route for the selective oxidation of a variety of thioethers to the corresponding sulfoxide or sulfone with 30% aqueous H2O2 in water, using newly synthesized peroxoniobium (pNb) complexes as catalysts, is described. The catalysts with formulas Na2[Nb(O2)3(arg)]·2H2O (arg = arginate) (NbA) and Na2[Nb(O2)3(nic)(H2O)]·H2O (nic = nicotinate) (NbN) have been synthesized from the reaction of sodium tetraperoxoniobate with 30% H2O2 and the respective organic ligand in an aqueous medium, and these have been comprehensively characterized by elemental analysis, spectral studies (FTIR, Raman, 1H NMR, 13C NMR and UV-vis), EDX analysis and TGA-DTG analysis. The density functional theory (DFT) method has been used to investigate the structure of the synthesized pNb complexes. The catalysts are physiologically safe and can be reused for at least six reaction cycles without losing their activity or selectivity. The oxidation is chemoselective for sulfides or sulfoxides leaving the C=C or alcoholic moiety unaffected. The developed methodologies, apart from being high yielding and straightforward, are completely free from halogen, organic co-solvent, or co-catalysts.
- Gogoi, Sandhya Rani,Boruah, Jeena Jyoti,Sengupta, Gargi,Saikia, Gangutri,Ahmed, Kabirun,Bania, Kusum K.,Islam, Nashreen S.
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p. 595 - 610
(2015/02/02)
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- Selective sulfoxidation with hydrogen peroxide catalysed by a titanium catalyst
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A moisture-tolerant cyclopentadienyl-silsesquioxane titanium complex efficiently catalyses the selective oxidation of various types of sulfides to either sulfoxides (TOFs up to 32 530 h-1) or sulfones with H2O2 (30% in water) under mild conditions.
- Postigo, Lorena,Ventura, Maria,Cuenca, Toms,Jimnez, Gerardo,Royo, Beatriz
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p. 320 - 324
(2015/02/02)
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- Efficient and selective hydrogen peroxide-mediated oxidation of sulfides in batch and segmented and continuous flow using a peroxometalate-based polymer immobilised ionic liquid phase catalyst
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The peroxometalate-based polymer immobilized ionic liquid phase catalyst [PO4{WO(O2)2}4]@PIILP has been prepared by anion exchange of ring opening metathesis-derived pyrrolidinium-decorated norbornene/cyclooctene copolymer and shown to be a remarkably efficient system for the selective oxidation of sulfides under mild conditions. A cartridge packed with a mixture of [PO4{WO(O2)2}4]@PIILP and silica operated as a segmented or continuous flow process and gave good conversions and high selectivity for either sulfoxide (92% in methanol at 96% conversion for a residence time of 4 min) or sulfone (96% in acetonitrile at 96% conversion for a residence time of 15 min). The immobilized catalyst remained active for 8 h under continuous flow operation with a stable activity/selectivity profile that allowed 6.5 g of reactant to be processed (TON = 46 428) while a single catalyst cartridge could be used for the consecutive oxidation of multiple substrates giving activity-selectivity profiles that matched those obtained with fresh catalyst.
- Doherty,Knight,Carroll,Ellison,Hobson,Stevens,Hardacre,Goodrich
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supporting information
p. 1559 - 1571
(2015/03/18)
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- Tungstate supported on periodic mesoporous organosilica with imidazolium framework as an efficient and recyclable catalyst for the selective oxidation of sulfides
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Abstract A catalyst based on immobilization of tungstate ions (WO42-) inside the mesochannels of periodic mesoporous organosilica comprising bridged ionic liquid (1,3-bis(3-trimethoxysilylpropyl)imidazolium chloride) has been synthesized and characterized. This catalyst was then employed for the selective oxidation of organic sulfides to the corresponding sulfoxides or sulfones. The final synthesized catalyst was characterized by various techniques such as nitrogen sorption analysis, transmission electron microscopy, and thermogravimetric analysis. The catalyst was also applied to the selective oxidation of sulfides containing readily oxidizable functional groups such as hydroxyl, allylic, and even challenging aliphatic sulfides. Interestingly, it was found that on changing the reaction medium from aqueous methanol to aqueous acetonitrile, the product selectivity was changed successfully from sulfoxide to sulfone with good to excellent yields. Moreover, the catalyst can also be recovered and reused efficiently in nine subsequent reaction cycles without any remarkable decrease in the catalyst activity and selectivity.
- Karimi, Babak,Khorasani, Mojtaba,Bakhshandeh Rostami, Fatemeh,Elhamifar, Dawood,Vali, Hojatollah
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p. 990 - 999
(2015/06/08)
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- Cobalt(II), copper(II), zinc(II) and palladium(II) Schiff base complexes: Synthesis, characterization and catalytic performance in selective oxidation of sulfides using hydrogen peroxide under solvent-free conditions
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An asymmetric bidentate Schiff-base ligand (HL: 2-tert-butyliminomethyl-phenol) was prepared from the reaction of salicylaldehyde and tert-butylamine. Cobalt(II), copper(II), zinc(II) and Pd(II) complexes, CoL2, CuL2, ZnL2 and PdL2, were synthesized from the reaction of CoCl2·6H2O, CuCl2·2H2O, Zn(NO3)2·6H2O and PdCl2 with the bidentate Schiff base ligand HL in methanol. The ligand and its metal complexes were characterized by elemental analysis (CHN), FT-IR and UV-Vis spectroscopy. In addition, 1H and 13C NMR techniques were employed for characterization of the ligand (HL) and the diamagnetic complexes (ZnL2 and PdL2). The molecular structures of all the complexes were determined by the single crystal X-ray diffraction technique. The crystallographic data reveal that in all the complexes the metal centers are four-coordinated by two phenolate oxygen and two imine nitrogen atoms of two Schiff base ligands. The geometry around the metal center in the CoL2, CuL2 and ZnL2 complexes is a distorted tetrahedral and for PdL2 it is square-planar. The catalytic activity of these complexes has been evaluated for the selective oxidation of sulfides with the green oxidant 35% aqueous H2O2 under solvent free conditions. For all the catalysts, using optimized reaction conditions, different sulfides were converted to the corresponding sulfones. ZnL2 showed a higher catalytic performance for the oxidation of the different sulfides to the corresponding sulfones.
- Khorshidifard, Mahsa,Rudbari, Hadi Amiri,Askari, Banafshe,Sahihi, Mehdi,Farsani, Mostafa Riahi,Jalilian, Fariba,Bruno, Giuseppe
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- Selective Synthesis of Sulfoxides through Oxidation of Sulfides with Sodium Hypochlorite Pentahydrate Crystals
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Oxidation of sulfides with sodium hypochlorite pentahydrate crystals (1.1 equiv) in an aqueous acetonitrile solution selectively produces the corresponding sulfoxides in high yields. This procedure is catalyst-free and environmentally benign.
- Okada, Tomohide,Matsumuro, Hiroaki,Kitagawa, Saori,Iwai, Toshiaki,Yamazaki, Kento,Kinoshita, Yukari,Kimura, Yoshikazu,Kirihara, Masayuki
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p. 2547 - 2552
(2015/11/16)
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- Suzuki-Miyaura Coupling Reactions of Conjunctive Reagents: 2-Borylated Allylic Sulfones
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In support of various efforts in our group, we developed methods for the convenient Suzuki-Miyaura coupling of borylated allylic sulfones with various electrophiles in both inter- and the less common intramolecular modes. The procedure facilitates the preparation of a wide variety of sulfones in a straightforward fashion, including six- through eight-membered rings.
- Altenhofer, Erich F.,Harmata, Michael
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p. 8168 - 8174
(2015/09/01)
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- Tris(hydroxymethyl)aminomethane modified layered double hydroxides greatly facilitate polyoxometalate intercalation
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Polyoxometalate (POM) intercalation to layered double hydroxides (LDHs) has been greatly restricted by the geometry, charge and size of POMs. We report herein, for the first time, the intercalation of Na3[PW12O40]·15H2O into tris(hydroxymethyl)-aminomethane (Tris) modified layered double hydroxides (Tris-LDH-CO3) using an ion exchange method, resulting in the formation of novel intercalated Tris-LDH-PW12 under ambient conditions without the necessity of degassing CO2. Theoretical calculations show the decreased energy and the slightly distorted LDH layer after Tris modification, indicating that the Tris-modified LDH layers greatly facilitate the intercalation of PW12. Further application of Tris-LDH-PW12 for oxygenation of sulfides shows highly efficient and selective catalytic activities under mild conditions. The Tris-LDH-PW12 can be easily recovered and reused for more than 10 times without any obvious decrease of reactivity. This opens a completely new pathway for engineering POM-LDH advanced functional materials. This journal is
- Chen, Yang,Yan, Dongpeng,Song, Yu-Fei
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p. 14570 - 14576
(2015/02/19)
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