- Crystal and molecular structure of methyl-(4-chlorophenyl)sulfone
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Sulfones are known to be biologically active compounds. X-ray diffraction is used to determine the crystal and molecular structure of methyl-(4-chlorophenyl)sulfone. The closest molecules are in pairs oriented to each other by their chlorine atoms. The cr
- Adamovich,Mirskova,Zel′bst,Fundamensky
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- 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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- 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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- Synthesis of a light-harvesting ruthenium porphyrin complex substituted with BODIPY units. Implications for visible light-promoted catalytic oxidations
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A light-harvesting ruthenium porphyrin substituted covalently with four boron-dipyrrin (BODIPY) moieties has been synthesized and studied. The resulting complex showed an efficient decarbonylation reaction predominantly due to a photo-induced energy transfer process. Chemical oxidation of the ruthenium(ii) BODIPY-porphyrin afforded a high-energytrans-dioxoruthenium(vi) species that is one order of magnitude more reactive towards alkene oxidation than those analogues supported by conventional porphyrins. In the presence of visible light, the ruthenium(ii) BODIPY-porphyrin displayed remarkable catalytic activity toward sulfide oxidation and alkene epoxidation using iodobenzene diacetate [PhI(OAc)2] and 2,6-dichloropyridineN-oxide (Cl2pyNO) as terminal oxidants, respectively. The findings in this work highlight that porphyrin-BODIPY conjugated metal complexes are potentially useful for visible light-promoted catalytic oxidations.
- Malone, Jonathan,Klaine, Seth,Alcantar, Christian,Bratcher, Fox,Zhang, Rui
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p. 4977 - 4985
(2021/03/26)
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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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- Air atmospheric photocatalytic oxidation by ultrathin C,N-TiO2nanosheets
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Herein, we demonstrate the highly efficient photocatalytic sulfide oxidation reaction under mild conditions,i.e.in air, at room temperature and in the absence of a sacrificial reagent, co-catalyst or redox mediator, by using ultrathin C,N-TiO2nanosheets as a photocatalyst.
- Cheng, Xiuyan,Zhang, Jianling,Liu, Lifei,Zheng, Lirong,Zhang, Fanyu,Duan, Ran,Sha, Yufei,Su, Zhuizhui,Xie, Fei
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supporting information
p. 1165 - 1170
(2021/02/26)
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- COVALENT ORGANIC FRAMEWORKS AND APPLICATIONS AS PHOTOCATALYSTS
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Described herein are covalent organic frameworks. The covalent organic frameworks have unique structural and physical properties, which lends them to be versatile in a number of different applications and uses. In one aspect, the covalent organic frameworks are composed of a plurality of fused aromatic groups and electron-deficient chromophores. The covalent organic frameworks are useful as photocatalysts in a number of different applications.
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Paragraph 00146; 00169
(2021/05/21)
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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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- Method for catalytically oxidizing thioether to sulphone
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The invention discloses a method for catalytically oxidizing thioether to sulphone. In this method, thioether is added to an ethanol solution. H2 O2 The nitrogen-nitrogen co-doped graphene catalyst is reacted at room temperature to obtain sulfone. The method is simple and convenient to operate, environment-friendly in reaction process, low in production cost, free of metal catalysts, free of secondary pollution, mild in reaction conditions, low in catalyst consumption, high and product yield and the like.
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Paragraph 0031-0034
(2021/11/19)
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- Synergistic cooperative effect of CF3SO2Na and bis(2-butoxyethyl)ether towards selective oxygenation of sulfides with molecular oxygen under visible-light irradiation
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A safe, practical and eco-friendly method for the switchable synthesis of sulfoxides and sulfones through visible-light-initiated oxygenation of sulfides at ambient temperature under transition-metal-, additives-free and minimal solvent conditions. The synergistic catalytic efforts between CF3SO2Na and 2-butoxyethyl ether represents the key promoting factor for the reaction. This journal is
- Liu, Kai-Jian,Wang, Zheng,Lu, Ling-Hui,Chen, Jin-Yang,Zeng, Fei,Lin, Ying-Wu,Cao, Zhong,Yu, Xianyong,He, Wei-Min
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supporting information
p. 496 - 500
(2021/01/28)
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- Electrochemical oxygenation of sulfides with molecular oxygen or water: Switchable preparation of sulfoxides and sulfones
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A practical and eco-friendly method for the controllable aerobic oxygenation of sulfides by electrochemical catalysis was developed. The switchable preparation of sulfoxides and sulfones was effectively controlled by reaction time, in which both molecular oxygen and water can be used as the oxygen source under catalyst and external oxidant-free conditions. The electrochemical protocol features a broad substrate scope and excellent site selectivity and is successfully applied to the modification of some sulfide-containing pharmaceuticals and their derivatives. This journal is
- Li, Jin-Heng,Li, Yang,Sun, Qing,Xue, Qi,Zhang, Ting-Ting
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supporting information
p. 10314 - 10318
(2021/12/17)
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- Sulfoxide and Sulfone Synthesis via Electrochemical Oxidation of Sulfides
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The oxidation of diaryl sulfides and aryl alkyl sulfides to the corresponding sulfoxides and sulfones under electrochemical conditions is reported. Sulfoxides are selectively obtained in good yield under a constant current of 5 mA for 10 h in DMF, while sulfones are formed as the major product under a constant current of 10 or 20 mA for 10 h in MeOH. The oxygen of both the sulfoxide and sulfone function is derived from water.
- Lee, Sunwoo,Park, Jin Kyu
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p. 13790 - 13799
(2021/10/12)
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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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- Modulation of photochemical oxidation of thioethers to sulfoxides or sulfones using an aromatic ketone as the photocatalyst
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We have developed an eco-friendly and chemo-selective photocatalytic synthesis of sulfoxides or sulfones via oxidation of sulfides (thioethers) at ambient temperature using air or O2 as the oxidant. An inexpensive thioxanthone was used as the photocatalyst. Our method offers excellent chemical yields and good functional group tolerance. The hydrogen bonding between hexafluoro-2-propanol (HFIP) and sulfoxides may play an important role in minimizing the over-oxidization of sulfoxides.
- Zhao, Bin,Hammond, Gerald B.,Xu, Bo
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supporting information
(2021/09/13)
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- Biocatalytic Oxidation of Sulfides to Sulfones
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This paper describes a method for the biocatalytic oxidation of sulfides. During the screening of microorganisms using pure cultures of bacteria and fungi for the oxidation of sulfides, it was observed that a number of strains of microorganisms, were able to oxidize various sulfides (1-4), but the desired sulfoxide was either not obtained or obtained only as a minor product. A close observation of the reaction showed complete oxidation and thus sulfone (5-8) formation had occurred in these cases. Sulfones are used to stabilize intermediates like α-radicals, α-anions etc. and also used as cationic synthons in many known reactions. This prompted us to explore the sulfone synthesis by biocatalytic route. Approximately 20% of the strains tested (400 bacterial and 200 fungal) showed the formation of sulfone with conversion rate varying from 3 to 100% based on TLC analysis. There were two strains of fungi, Aspergillus ochraceus MTCC 5245 and Penicillium Funiculosum MTCC 5246 which showed excellent biocatalytic activity for oxidation sulfides to corresponding sulfones in high yield. In all these strains, the product was different from corresponding standard sulfoxide prepared by oxidation with m-chloroperbenzoic acid but well corresponded with the standard sample of sulfone prepared by oxidation of the corresponding sulfides with oxone. The identity of sulfones in all cases was confirmed by 1H NMR. Published by Oriental Scientific Publishing Company
- Dhiman, Shefali
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p. 250 - 255
(2021/03/29)
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- PROTEIN-MACROMOLECULE CONJUGATES AND METHODS OF USE THEREOF
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The present disclosure provides protein-macromolecule conjugates, releasable linkers, and macromolecules, as defined herein. The disclosed conjugates provide unique properties that are based at least upon the properties of linker and number of linker-Macromolecule moieties. Also provided herein are a method of synthesis and use of conjugates in treating diseases and disorders.
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Paragraph 0394; 0396
(2021/04/10)
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- Metal-Free Synthesis of Sulfones and Sulfoxides through Aldehyde-Promoted Aerobic Oxidation of Sulfides
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Metal-free aerobic oxidation of aryl sulfides to sulfoxides and sulfones has been developed in the presence of aliphatic aldehydes with excellent selectivity and yields. The reaction proceeded under mild conditions with the catalysis of N-hydroxyphthalimide (NHPI). Control experiments indicated that the reaction underwent a free radical pathway with the acylperoxyl radicals generated from aldehydes in situ as the key intermediates. The aromatic aldehydes were less efficient in the sulfide oxidation, which might be explained by the fact that the aromatic ring dispersed the electrons of free radicals and thus weakened the attacking ability of peroxy free radicals. Graphic Abstract: [Figure not available: see fulltext.]
- Li, Haoran,Wang, Lingyao,Yao, Jia,Zhang, Yuanbin
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- Highly efficient and selective aqueous aerobic oxidation of sulfides to sulfoxides or sulfones catalyzed by tungstate-functionalized nanomaterial
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A Br?nsted acidic ionic solid comrising tungstate-functionaized polyorganosiloxane framework (PMO-IL-WO42?) efficiently catalysed aerobic oxidation of sulfides in aqueous medium. The catalyst can selectively produce sulfoxides or sulfones by running the reaction at room temperature or 50 °C, respectively. Because of the ionic liquid-based charged surface containing hydrophobic organic functional groups and hydrophilic sulfonic acid group, the synergestic hydrophobic/hydrophilic and redox effect of PMO-IL-WO42- as water-friendly interfacial nanocatalyst simplifies and enhances the activity and selectivity toward the target sulfoxides or sulfones in water. Moreover, the PMO-IL-WO42- nanocatalyst exhibited outstanding stability and activity and can be recycled eight reaction runs without any significant activity and selectivity loss.
- Luque, Rafael,Rajabi, Fatemeh,Vessally, Esmail,Voskressensky, Leonid
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- Primary Sulfonamide Functionalization via Sulfonyl Pyrroles: Seeing the N?Ts Bond in a Different Light
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Despite common occurrence in molecules of value, methods for transforming sulfonamides are distinctly lacking. Here we introduce easy-to-access sulfonyl pyrroles as synthetic linchpins for sulfonamide functionalization. The versatility of the sulfonyl pyrrole unit is shown by generating a variety of products through chemical, electrochemical and photochemical pathways. Preliminary results on the direct functionalization of primary sulfonamides are also provided, which may lead to new modes of activation.
- Ozaki, Tomoya,Yorimitsu, Hideki,Perry, Gregory J. P.
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p. 15387 - 15391
(2021/10/04)
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- Method for synthesizing aryl alkyl sulfone compound by promoting oxidation of aryl alkyl thioether compound through visible light
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The invention discloses a method for synthesizing an aryl alkyl sulfone compound by promoting oxidation of an aryl alkyl thioether compound through visible light. The method comprises the following steps of: performing one-pot reaction on an aryl alkyl thioether compound and sodium trifluoromethanesulfinate in a diethylene glycol dibutyl ether solution system under the conditions of oxygen-containing atmosphere and 385-390 nm purple light irradiation to generate the aryl alkyl sulfone compound. The method has the advantages of mild conditions, simple operation, environmental protection, easilyavailable raw materials, excellent compatibility of substrate functional groups, high reaction yield and the like.
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Paragraph 0049-0052; 0057-0060; 0065-0067
(2021/02/13)
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- Preparation method of methyl sulfone compound
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The invention discloses a synthesis method of a methyl sulfone compound, which comprises the following steps: by using an iodinated compound as a substrate, adding a sulfite compound into the substrate, and using a 1, 4-dioxane solution as a solvent, heating under the protection of nitrogen under the actions of a silicon reagent, a phase transfer catalyst and a palladium catalyst to obtain a crudeproduct; then purifying the crude product, firstly filtering the crude product, and removing the solvent to obtain residues; carrying out silica gel column chromatography on the residues, leaching with eluent, and collecting effluent; combining the effluent containing the product; and concentrating the combined effluent to remove the solvent, and finally carrying out vacuum drying to obtain the target product. The method has the advantages of simple process flow, easiness in product purification, environmental safety and high yield.
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Paragraph 0005; 0023
(2021/02/24)
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- Selectivity switch in the aerobic oxygenation of sulfides photocatalysed by visible-light-responsive decavanadate
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Nanometre-sized metal oxides are promising species for the development of visible-light-responsive photocatalysts for the selective transformation of organic functional groups. In this article, we report that decavanadate ([V10O28]6-, V10) behaved as an efficient visible-light-responsive photocatalyst in the product-selective oxygenation of sulfides achieved using O2 (1 atm) as the green oxidant. In particular, we revealed that visible-light-responsive photocatalysis of V10 showed remarkable activity for the oxygenation of structurally diverse sulfides to form the corresponding sulfones using O2 in methyl ethyl ketone (MEK). Furthermore, by simply adding water to the reaction mixture, the product selectivity of sulfide oxygenation can be significantly switched toward the production of sulfoxides, without concomitant loss of photocatalytic activity. Based on experimental evidence, we inferred the following mechanistic steps for this photocatalytic system: the aerobic oxygenation of sulfides to form the corresponding sulfoxides initiated by a visible-light-induced photoredox reaction of V10. As for the formation of sulfones, MEK-derived peroxide species as the co-catalysts are probably involved in the oxygenation of sulfoxides to sulfones. The selectivity switch of the V10-photocatalysed reaction brought about by water addition is most likely achieved by suppressing the formation of MEK-derived peroxide species. This journal is
- Li, Chifeng,Mizuno, Noritaka,Murata, Kei,Ishii, Kazuyuki,Suenobu, Tomoyoshi,Yamaguchi, Kazuya,Suzuki, Kosuke
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supporting information
p. 3896 - 3905
(2020/07/09)
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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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- Formation and kinetic studies of manganese(IV)-oxo porphyrins: Oxygen atom transfer mechanism of sulfide oxidations
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Visible light irradiation of photo-labile porphyrin-manganese(III) chlorates or bromates (2) produced manganese(IV)-oxo porphyrins [MnIV(Por)(O)] (Por = porphyrin) (3) in three porphyrin ligands. The same oxo species 3 were also formed by chemical oxidation of the corresponding manganese(III) precursors (1) with iodobenzene diacetate, i.e. PhI(OAc)2. The systems under study include 5,10,15,20-tetra(pentafluorophenyl)porphyrin?manganese(IV)-oxo (3a), 5,10,15,20-tetra(2,6-difluorophenyl)porphyrin?manganese(IV)-oxo (3b), and 5,10,15,20-tetramesitylporphyrin?manganese(IV)-oxo (3c). As expected, complexes 3 reacted with thioanisoles to produce the corresponding sulfoxides and over-oxidized sulfones. The kinetics of oxygen atom transfer (OAT) reactions of these generated 3 with aryl sulfides were studied in CH3CN solutions. Second-order rate constants for sulfide oxidation reactions are comparable to those of alkene epoxidations and activated C[sbnd]H bond oxidations by the same oxo species 3. For a given substrate, the reactivity order for the manganese(IV)-oxo species was 3a > 3b > 3c, consistent with expectations on the basis of the electron-withdrawing capacity of the porphyrin macrocycles. Free-energy Hammett analyses gave near-linear correlations with σ values, indicating no significant positive charge developed at the sulfur during the oxidation process. The mechanistic results strongly suggest [MnIV(Por)(O)] reacts as a direct OAT agent towards sulfide substrates through a manganese(II) intermediate that was detected in this work. However, an alternative pathway that involves a disproportionation of 3 to form a higher oxidized manganese(V)-oxo species may be significant when less reactive substrates are present. The competition product studies with the Hammett correlation plot confirmed that the observed manganese(IV)-oxo species is not the true oxidant for the sulfide oxidations catalyzed by manganese(III) porphyrins with PhI(OAc)2.
- Klaine, Seth,Bratcher, Fox,Winchester, Charles M.,Zhang, Rui
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- Iridium complex-linked porous organic polymers for recyclable, broad-scope photocatalysis of organic transformations
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Two rigid porous organic polymers (Ir-POP-1 and Ir-POP-2) were prepared from the coupling reactions of tetraphenylmethane tetraborate and two [Ir(ppy)2(dtbbpy)]+-based bitopic linkers and applied as heterogeneous visible-light photocatalysts for organic transformations. Ir-POP-2 was found to exhibit high catalytic activity for a wide range of organic reactions, which include Smiles-Truce rearrangement of alkyliodides, desulfurative conjugate addition to Michael acceptors, and aerobic oxidations of sulfides and arylboronic acids. For all the transformations, Ir-POP-2 could achieve heterogeneous photocatalytic efficiency that rivals that of the homogeneous prototype iridium complexes. This remarkably high photocatalytic performance has been attributed to the large pore size of the conjugated backbone. The new heterogeneous photocatalyst was also highly stable to achieve good recyclability for all the studied reactions and could be reused eight to nineteen times.
- Xu, Zi-Yue,Luo, Yi,Zhang, Dan-Wei,Wang, Hui,Sun, Xing-Wen,Li, Zhan-Ting
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supporting information
p. 136 - 143
(2020/01/21)
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- Visible light generation of chromium(V)-oxo salen complexes and mechanistic insights into catalytic sulfide oxidation
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Visible light irradiation of the photo-labile salen-chromium(III) chlorate or bromate precursors produced salen-chromium(V)-oxo complexes that were spectroscopically and kinetically indistinguishable from those formed by chemical oxidation of chromium(III) salens with PhI(OAc)2. The photochemistry observed in this work is ascribed to the heterolytic cleavage of the O-X bond in the apical counterion that results in a two-electron oxidation of the metal to form the chromium(V)-oxo species. Second-order rate constants for oxidation reactions of 3 with organic substrates were determined under pseudo-first order condition, and particularly low level of reactivity for sulfide oxidations was observed. In this study, chromium(III) salen complexes effectively catalyzed the oxidation of aryl sulfides into sulfoxides with PhI(OAc)2 in the presence of a small amount of water. The competition product studies with the Hammett correlation plot indicated that the observed chromium(V)-oxo species is not likely to serve as the major oxidant for the sulfide oxidations catalyzed by chromium(III) salens with PhI(OAc)2.
- Dames, Angeline,Fung Lee, Ngo,Klaine, Seth,Zhang, Rui
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- Accurate Regulating of Visible-Light Absorption in Polyoxotitanate-Calix[8]arene Systems by Ligand Modification
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With use of a macrocyclic polyphenol, tert-butylcalix[8]arene (TBC[8]), as ligands, a series of TBC[8]-stabilized {Ti4O2}clusters, containing penta- and hexacoordinated Ti centers, were synthesized. Such complexes are "core-shell" shaped containing a {Ti4O2} core arranged in a zigzag fashion. While outer walls of the clusters are decorated by deprotonated TBC[8], their upper and lower surfaces can be modified by various O- or N-donor ligands, and the ratio of the penta- and hexacoordinated Ti(IV) centers in the {Ti4O2} core can be precisely regulated from 4:0, to 3:1, to 2:2, to 1:3, and finally to 0:4. The combined coordination of different ligands in the axial direction shows significant influence on the adsorption of the TBC[8]-Ti4 system in the visible-light region, and their absorption edge can be precisely regulated from 600 to 700 nm. The above structural functionalization in the TBC[8]-Ti4 system also tunes their photocatalytic H2 production activities and oxidative desulfurization ability. Thus, for the first time, by confining the polyoxotitanium cluster in macrocyclic molecules, we provide an example of understanding the structure-property relationship of titanium-oxygen materials by ligand modification.
- Liu, Chao,Yang, Xin-Xue,Yi, Xiao-Yi,Yu, Wei-Dong
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- Synthesis method of sulfone compound
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The invention discloses a synthesis method of a sulfone compound. The synthesis method specifically comprises the following steps: taking a compound shown as formula (I) as a reaction raw material, Ru/C as a catalyst, NaIO4 as an oxidant and water as a solvent, reacting at room temperature, and after the reaction is finished, carrying out after-treatment on an obtained reaction solution to obtainthe sulfone compound shown as formula (II), wherein the use amount of Ru/C is 0.5-2% of the molar amount of the compound shown in the formula (I) in terms of the molar amount of Ru; the molar amount of NaIO4 is 50-150% of the molar amount of the compound represented by formula (I). Under normal temperature conditions, cheap ruthenium carbon is oxidized by sodium periodate to generate ruthenium tetroxide, so that a thioether compound is further oxidized to synthesize the sulfone compound, the yield is close to 100 %, the subsequent treatment is simple, and a pure product can be obtained withoutcomplex separation and purification. Therefore, the method is more efficient, faster, more environmentally friendly and milder.
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Paragraph 0045-0049
(2020/01/25)
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- Copper(ii)-containing tungstotellurates(vi): Syntheses, structures and their catalytic performances in selective oxidation of thioethers
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We report the syntheses and structures of two new copper(ii)-containing tungstotellurates(vi) Na12[TeVI2W8O38Cu2(H2O)2]·7H2O (Te2W8Cu2) and Na6[TeVIW6O24Cu(NH2CH2CO2)2]·6H2O (TeW6Cu). The two compounds were synthesized by a simple one-pot method and characterized by single-crystal X-ray diffraction (XRD), powder XRD, FT-IR spectroscopy, elemental analysis, and thermogravimetric analysis in the solid state. Furthermore, their catalytic properties for the selective oxidation of thioethers were also studied systematically. The catalytic experiment results indicate that the tungstotellurate(vi) Te2W8Cu2 is an effective heterogeneous catalyst for the selective oxidation of thioethers to sulfoxides or sulfones by an H2O2 oxidant at room temperature. Under the ambient conditions, Te2W8Cu2 can convert 99percent of methyl(phenyl)sulfane to sulfoxides or sulfones with 96percent or 99percent selectivity, respectively, and the utilization rate of H2O2 is up to 80percent. Furthermore, Te2W8Cu2 as a heterogeneous catalyst is stable in the reaction and could be reused at least five cycles with conserved activity.
- Hu, Changwen,Li, Peihe,Li, Xuanyao,Lin, Zhengguo,Liu, Jinghai
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p. 22515 - 22521
(2020/07/03)
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- Selective oxidation of (hetero)sulfides with molecular oxygen under clean conditions
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The development of eco-friendly and switchable catalytic systems for the conversion of a sole raw-material into distinct high-value products is a particularly attractive concept and a daunting synthetic challenge. In the present work, the first example of efficient and selective oxidation of sulfides to sulfones and sulfoxides using molecular oxygen under clean conditions was established.
- Liu, Kai-Jian,Deng, Ji-Hui,Yang, Jie,Gong, Shao-Feng,Lin, Ying-Wu,He, Jun-Yi,Cao, Zhong,He, Wei-Min
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supporting information
p. 433 - 438
(2020/02/13)
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- Oxidation of aromatic sulfides with molecular oxygen: Controllable synthesis of sulfoxides or sulfones
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The recent development of selective oxidation of aromatic sulfides with molecular oxygen was highlighted. The sulfoxides and sulfones could be obtained by simply switching the reaction media, i.e., bis(2-butoxyethyl)ether (BBE) or poly(ethylene glycol)dimethyl ether (PEGDME). The application of the high-boiling-point polyether as an initiator and green media can eliminate the need of large quantities of additives and volatile solvents. This strategy represents an economic and eco-friendly method that could find potential applications.
- Tang, Lili,Du, Kejie,Yu, Bing,He, Liangnian
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p. 2991 - 2992
(2020/03/24)
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- Inorganic-organic hybrid polyoxovanadates based on [V4O12]4-or [VO3]22-clusters: Controllable synthesis, crystal structures and catalytic properties in selective oxidation of sulfides
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By rationally controlling hydrothermal conditions, three new inorganic-organic hybrid polyoxovanadates (POVs) [Ni2(1-vIM)7H2O][V4O12]·H2O (1), [Cu2(1-vIM)8][V4O12]·H2O (2) and [Co(1-vIM)H2O][VO3]2 (3) (1-vIM = 1-vinylimidazole) have been synthesized and thoroughly characterized by single X-ray diffraction (SXRD), powder X-ray diffraction (PXRD), infrared spectroscopy (FT-IR), and elemental analyses (EA). Interestingly, complexes 1 and 2 have similar structures including [V4O12]4- clusters; complex 3, however, was isolated as a structure by including the [VO3]22- cluster under a different synthetic condition compared with those of 1 and 2. Both complexes 1 and 2 display an interesting 3D supramolecular structure, and complex 3 shows a 2D two parallel networks supramolecular structure linked by a [Co2O2] unit due to the different coordination environments of the central metals. Three inorganic-organic hybrid POVs asheterogeneous catalysts are active in the selective oxidation of sulfides to produce sulfoxides or sulfones with high conversion and high selectivity (up to 99.5 for sulfoxides and 98.5% for sulfones respectively catalyzed by 1). Complex 1 is also used as catalyst in the oxidative CEES (2-chloroethyl ethyl sulfide, a sulfur mustard simulant) abatement with high activity and selectivity towardthe corresponding sulfoxide. Moreover, complex 1 can be reused at least three times in sulfoxidationreactions without losing its activity.
- Guo, Daigaojie,Han, Yinfeng,He, Guofang,Hu, Changwen,Huang, Xianqiang,Li, Jikun,Wang, Congcong,Wei, Chuanping,Zhang, Jianping
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p. 14148 - 14157
(2020/11/02)
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- The mutagenesis of a single site for enhancing or reversing the enantio- or regiopreference of cyclohexanone monooxygenases
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The mutagenesis of a "second sphere"switch residue of CHMOAcineto could control its enantio- and regiopreference. Replacing phenylalanine (F) at position 277 of CHMOAcineto into larger tryptophan (W) enabled a significant enhancement of enantio- or regioselectivity toward structurally diverse substrates, moreover, a complete reversal of enantio- or regiopreference was realized by mutating F277 into a range of smaller amino acids (A/C/D/E/G/H/I/K/L/M/N/P/Q/R/S/T/V).
- Hu, Yujing,Xu, Weihua,Hui, Chenggong,Xu, Jian,Huang, Meilan,Lin, Xianfu,Wu, Qi
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supporting information
p. 9356 - 9359
(2020/11/02)
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- General sulfone construction: Via sulfur dioxide surrogate control
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A highly efficient one-step synthesis of alkyl-alkyl and aryl-alkyl sulfones with a facile combination of halides, sulfur dioxide surrogates and phosphate esters is described. When thiourea dioxide was employed as a reductive sulfur dioxide surrogate, alkyl-alkyl sulfones were obtained under transition metal free conditions. Aryl-alkyl sulfones were obtained with an extremely low catalytic loading (0.2 mol%) via altering the mask of sulfur dioxide surrogates to sodium dithionite. A phosphate ester was employed as a stable and readily available alkyl source. Notably, this protocol has been applied to the late-stage modification of natural products and bioactive molecules.
- Chen, Shihao,Li, Yaping,Wang, Ming,Jiang, Xuefeng
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supporting information
p. 322 - 326
(2020/02/13)
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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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- Ionic Liquid Stabilized Niobium Oxoclusters Catalyzing Oxidation of Sulfides with Exceptional Activity
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We present here a new class of niobium oxoclusters that are stabilized effectively by carboxylate ionic liquids. These functionalized ILs are designated as [TBA][LA], [TBA][PA], and [TBA][HPA] in this work, in which TBA represents tetrabutylammonium and LA, PA, and HPA refer to lactate, propionate, 3-hydroxypropionate anions, respectively. The as-synthesized Nb oxoclusters have been characterized by use of elemental analysis, NMR, IR, XRD, TGA, HRTEM. It was found that [TBA][LA]-stabilized Nb oxoclusters (Nb?OC@[TBA][LA]) are uniformly dispersed with an average particle size of 2–3 nm and afforded exceptionally high catalytic activity for the selective oxidation of various thioethers. The turnover number with Nb?OC@[TBA][LA] catalyst was over 56 000 at catalyst loading as low as 0.0033 mol % (1 ppm). Meantime, the catalyst also showed the high activity for the epoxidation of olefins and allylic alcohols by using only 0.065 mol % of catalyst (50 ppm). The characterization of 93Nb NMR spectra revealed that the Nb oxoclusters underwent structural transformation in the presence of H2O2 but regenerated to their initial state at the end of the reaction. In particular, the highly dispersed Nb oxoclusters can absorb a large amount of polar organic solvents and thus were swollen greatly, which exhibited “pseudo” liquid phase behavior, and enabled the substrate molecules to be highly accessible to the catalytic center of Nb oxocluster units.
- Zhou, Qingqing,Ye, Man,Ma, Wenbao,Li, Difan,Ding, Bingjie,Chen, Manyu,Yao, Yefeng,Gong, Xueqing,Hou, Zhenshan
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p. 4206 - 4217
(2019/03/26)
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- Selective catalytic oxidation of sulfides to sulfoxides or sulfones over amorphous Nb2O5/AC catalysts in aqueous phase at room temperature
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Selective oxidation of sulfides into sulfoxides or sulfones is an important transformation in organic synthesis. Activated carbon supported Nb-based catalysts were prepared by the impregnation method and then characterized by the XRD, TEM and XPS. The characterization results indicate Nb species is amorphous Nb2O5. The catalysts were applied for the catalytic oxidation of sulfides in aqueous phase with H2O2 as the oxidant. Sulfides could be converted into the corresponding sulfoxides or sulfones with high conversion and selectivity at room temperature. The recycling experiments showed the Nb2O5/AC catalysts exhibited good reusability. They could be recycled for 10 times without obvious loss of activity and selectivity.
- Zhang, Junjie,Jiang, Tingting,Mai, Yuliang,Wang, Xi,Chen, Jiazhi,Liao, Bing
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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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- Discovery of a New Family of Polyoxometalate-Based Hybrids with Improved Catalytic Performances for Selective Sulfoxidation: The Synergy between Classic Heptamolybdate Anions and Complex Cations
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A series of functional cation-regulated isopolymolybdate-based organic-inorganic hybrid compounds, Na2H2[Mo4O12(C8H17O5N)2]·10H2O (1), Na2[M(Bis-tris)(H2O)]2[Mo7O24]·10H2O [M = Cu, 2; Ni, 3; Co, 4; Zn, 5; Bis-tris = 2,2-Bis(hydroxymethyl)-2,2′,2″-nitrilotriethanol], and (NH4)2[M(Bis-tris)(H2O)]2[Mo7O24]·6H2O (M = Zn, 6; Cu, 7), were synthesized and characterized toward advanced molecular catalyst design. Compound 1 is a covalently bonded adduct, and its self-assembly process can be probed by electrospray ionization mass spectrometry (ESI-MS). Compounds 2-7 are polyoxometalate (POM)-based hybrids containing classic heptamolybdate anions and complex cations with Bis-tris ligands. All of these compounds showed remarkable catalytic effects for selective sulfide oxidation. To the best of our knowledge, compound 5 presents the best catalytic activity so far among the reported hybrid materials with common easily synthesized small-molecule POM clusters and also exhibits outstanding reliability. The conclusion of the catalytic effect is drawn from the results that Zn-based compounds have better catalytic effects than other transition-metal-containing compounds and the compound constructed by Na+ has higher catalytic activity than that constructed by NH4 +. The mechanism studies show that the improvements of the catalytic performance are caused by the synergy between classic heptamolybdate anions and complex cations. ESI-MS data and UV-vis spectra revealed that the POM anions can form intermediate peroxomolybdenum units during catalytic reaction. Further, the combination of the substrate thioanisole with complex cations was characterized by NMR experiments and UV-vis spectra. Thus, a new synergistic mechanism of anions and cations is proposed in which the activated thioanisole is used as a nucleophile to attack the peroxomolybdenum bonds, and this provides a new strategy in the design of reliable POM-based catalysts.
- Zhang, Yin,Yu, Wei-Dong,Li, Bin,Chen, Zheng-Fan,Yan, Jun
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supporting information
p. 14876 - 14884
(2019/11/05)
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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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- Method for preparing aryl sulfone compound as well as method for extracting catalyst and aryl sulfone compound
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The invention provides a preparation method of an aryl sulfone compound, which is characterized in that in an organic solvent and under an aerobic atmosphere, a catalytic system composed of a metal-ligand-TEMPO is used for catalytic oxidation of a thioether compound to obtain the aryl sulfone compound. The preparation method is simple, green, and efficient, the reaction condition is mild, and theapplication range is wide; the invention also provides a method for extracting a catalyst and the product aryl sulfone compound used in the preparation process. The ethyl acetate is added to a reaction mixture, steps of filtering and condensation under reduced pressure are carried out to obtain a filtrate and the catalyst, and silica gel column chromatography and concentration extraction are carried out to obtain the aryl sulfone compound. The extraction method is simple, and the extracted catalyst has high activity and good cycle stability, and the extraction rate of the product aryl sulfonecompound is high.
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Paragraph 0104-0107
(2019/02/13)
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- HETEROCYCLIC CARBOXYLIC ACID AMIDE LIGAND AND APPLICATIONS THEREOF IN COPPER CATALYZED COUPLING REACTION OF ARYL HALOGENO SUBSTITUTE
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Provided are a heterocyclic carboxylic acid amide ligand and applications thereof in a copper catalyzed coupling reaction. Specifically, provided are uses of a compound represented by formula (I), definitions of radical groups being described in the specifications. The compound represented by formula (I) can be used as the ligand in the copper catalyzed coupling reaction of the aryl halogeno substitute, and is used or catalyzing the coupling reaction for forming the aryl halogeno substitute having C—N, C—O, C—S and other bonds.
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Paragraph 0293-0294
(2019/05/15)
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- Aryl Methyl Sulfone Construction from Eco-Friendly Inorganic Sulfur Dioxide and Methyl Reagents
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A three-component cross-coupling protocol of boronic acid, sodium metabisulfite, and dimethyl carbonate was developed for the construction of significant functional methyl sulfones, in which introduction of sulfur dioxide at the last stage was successfully achieved in one step. Inorganic sodium metabisulfite was used as an eco-friendly sulfur dioxide source. Green dimethyl carbonate was employed as methyl reagent in this transformation. Diverse functional methyl sulfones were obtained from various readily available boronic acids. Notably, the last-stage modification of pharmaceuticals and the synthesis of Firocoxib were efficiently established through this strategy.
- Wang, Ming,Zhao, Jiaoyan,Jiang, Xuefeng
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p. 3064 - 3068
(2019/02/19)
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- Insights from kinetic studies of photo-generated compound II models: Reactivity toward aryl sulfides
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Iron(IV)-oxo porphyrins [FeIV(Por)O] (Por = poprhyrin), commonly called compound II models, were produced in three electron-deficient ligands by visible light irradiation of highly photo-labile porphyrin-iron(III) bromates or chlorates. The kinetics of oxygen transfer atom (OAT) reactions with aryl sulfides by these photo-generated [FeIV(Por)O] (3) were studied in CH3CN solutions. The iron(IV)-oxo porphyrins under study include 5,10,15,20-tetra(2,6-dichlorophenyl)porphyrin-iron(IV)-oxo (3a), 5,10,15,20-tetra(2,6-difluorophenyl)porphyrin-iron(IV)-oxo (3b), and 5,10,15,20-tetra(pentafluorophenyl)porphyrin-iron(IV)-oxo (3c). As expected, complexes 3 were competent oxidants and reacted rapidly with thioanisoles to give the corresponding sulfoxides with minor over-oxidation sulfones. Apparent second-order rate constants determined under pseudo-first-order conditions for sulfide oxidation reactions are (9.8 ± 0.1) × 102–(3.7 ± 0.3) × 101 M?1 s?1, which are 3 to 4 orders of magnitude greater in comparison to those of alkene epoxidations and activated C–H bond oxidations by the same oxo species. Conventional Hammett analyses gave non-linear correlations, indicating no significant charge developed at the sulfur during the oxidation process. For a given substrate, the reactivity order for the iron(IV)-oxo species was 3c 3b 3a, which is inverted from expectations on the basis of the electron-withdrawing capacity of the porphyrin macrocycles. The absolute rate constants from kinetic studies provided insights into the transient oxidants in catalytic reactions under turnover conditions where actual reactive intermediates are not observable. Our kinetic and catalytic competition results strongly suggest that 3 may undergo a disproportionation reaction to form a higher oxidized iron(IV)-oxo porphyrin radical cations as the true oxidant.
- Lee, Ngo Fung,Patel, Dharmesh,Liu, Haiyan,Zhang, Rui
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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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- 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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- Synthesis and Pharmacological Activity of Tris(2-hydroxyethyl)ammonium 4-Chlorophenylsulfonylacetate
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Methods for the synthesis of 4-chlorophenylsulfonylacetic acid and its tris(2-hydroxyethyl)ammonium salt (“sulfacetamine”) were studied. The results of in vitro and in vivo experiments showed that sulfacetamine possesses high antithrombotic, antioxidant, hypocholesterolemic, immunostimulating, and protective-adaptive activities.
- Adamovich,Oborina,Mirskova
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p. 701 - 705
(2018/07/06)
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- A general electrochemical strategy for the Sandmeyer reaction
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Herein we report a general electrochemical strategy for the Sandmeyer reaction. Using electricity as the driving force, this protocol employs a simple and inexpensive halogen source, such as NBS, CBrCl3, CH2I2, CCl4, LiCl and NaBr for the halogenation of aryl diazonium salts. In addition, we found that these electrochemical reactions could be performed using anilines as the starting material in a one-pot fashion. Furthermore, the practicality of this process was demonstrated in the multigram scale synthesis of aryl halides using highly inexpensive graphite as the electrode. A series of detailed mechanism studies have been performed, including radical clock and radical scavenger study, cyclic voltammetry analysis and in situ electron paramagnetic resonance (EPR) analysis.
- Liu, Qianyi,Sun, Beiqi,Liu, Zheng,Kao, Yi,Dong, Bo-Wei,Jiang, Shang-Da,Li, Feng,Liu, Guoquan,Yang, Yang,Mo, Fanyang
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p. 8731 - 8737
(2018/12/10)
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- A Class of Amide Ligands Enable Cu-Catalyzed Coupling of (Hetero)aryl Halides with Sulfinic Acid Salts under Mild Conditions
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The amide derived from 4-hydroxy-l-proline and 2,6-dimethylaniline is a powerful ligand for Cu-catalyzed coupling of (hetero)aryl halides with sulfinic acid salts, allowing the formation of a wide range of (hetero)aryl sulfones from the corresponding (hetero)aryl halides at considerably low catalytic loadings. The coupling of (hetero)aryl iodides and sodium methanesulfinate proceeds at room temperature with only 0.5 mol % CuI and ligand, representing the first example for Cu-catalyzed arylation at both low catalytic loading and room temperature.
- Zhao, Jinlong,Niu, Songtao,Jiang, Xi,Jiang, Yongwen,Zhang, Xiaojing,Sun, Tiemin,Ma, Dawei
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p. 6589 - 6599
(2018/05/31)
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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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