- Hydrolytic stability and hydrogen peroxide activation of zirconium-based oxoclusters
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The hydrolytic stability of [Zr6(OH)4O4{O(O)CC(CH3)=CH2}12] (Zr6), and [Zr6O4(OH)4{O(O)CCH2CH=CH2}12]2·6[CH2=CHCH2C(O)OH] (Zr12) oxoclusters in different environments was thoroughly investigated by FTIR, Raman, and X-ray photoelectron spectroscopy (XPS). Specific information about the local structures around the Zr centers during the stability tests was achieved by in situ extended X-ray absorption fine structure (EXAFS) measurements, and the exact compositions were determined by inductively coupled plasma MS (ICP-MS) and elemental analysis. By this multidimensional spectroscopic approach, an overview on the structures formed after different treatments could be gained. The stability of the oxoclusters was then investigated in the presence of hydrogen peroxide, and the formation of peroxo-metal complexes was detected. Thus, a kinetic study was performed in acetonitrile to evaluate the performances of the oxoclusters as oxygen transfer catalysts. The oxidation of methyl p-tolyl sulfide to the corresponding sulfoxide and sulfone was chosen as a model reaction; in some cases, an interesting selectivity towards the formation of the sulfone was found over more than 4700 catalytic cycles.
- Faccioli, Francesco,Bauer, Matthias,Pedron, Danilo,Sorarù, Antonio,Carraro, Mauro,Gross, Silvia
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- Efficient oxidation of sulfides catalyzed by a temperature-responsive phase transfer catalyst [(C18H37)2(CH 3)2N]7 PW11O39 with hydrogen peroxide
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A temperature-responsive phase transfer catalyst [(C18H 37)2(CH3)2N]7PW 11O39, could act as an efficient catalyst for selective oxidation of sulfides with 30% aqueous H2O2. Various kinds of sulfides were successfully oxidized to their corresponding sulfones with over 96% yields in a relatively short time and mild conditions. During reaction at 333 K, the catalyst dissolved completely and the oxidation was conducted homogeneously. Before and after reaction, the catalyst was insoluble with cooling, so it is easily recovered and reused. The catalyst was characterized by elemental analysis, FT-IR and 31P NMR.
- Xue, Xiaoling,Zhao, Wei,Ma, Baochun,Ding, Yong
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- Evidence for cyclodextrin dioxiranes
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α-Cyclodextrin, β-cyclodextrin, 2,6-di-O-methyl-β-cyclodextrin, methyl-β-cyclodextrin and sucrose have been oxidised by aqueous bromine solution at neutral pH. Both ketone and carboxylic acid containing materials are among the products of the oxidations. For α-cyclodextrin there is clear 13C NMR evidence for the presence of a ketone group and its hydrate form. This together with the continued ability of the product to complex p-nitrophenol indicates that the ketone is present at the secondary rim of an intact cyclodextrin ring. A pH dependence for the reaction of bromine with cyclodextrin shows that the maximum rate of bromine loss roughly coincides with the maximum concentration of hypobromous acid, HOBr, indicating that this is the reactive species in these oxidations. The results are consistent with a mechanism involving attack by one of the secondary hydroxyls of cyclodextrin on HOBr, with Br- leaving to yield an intermediate dehydroxy hydroperoxy cyclodextrin that subsequently decomposes to a keto-cyclodextrin via a Kornblum-De La Mare-type reaction. An alternative pathway prevails when the reaction is carried out under alkaline conditions, where carboxylic acids are the principle products. The keto derivatives produced by bromine oxidation at neutral pH are capable of catalysing the oxidation of p-nitrophenol and aryl-alkyl sulfoxides by peroxomono-sulfate in an analogous way to cyclohexanone, which is known to form a dioxirane upon reaction with peroxomonosulfate. It is likely that dioxirane formation is responsible for the observed catalysis in the present case also.
- Deary, Michael E.,Davies, D. Martin
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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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- Chemistry of Oxaziridines. 10. Selective Catalytic Oxidation of Sulfides to Sulfoxides Using N-Sulfonyloxaziridines
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The chemoselective catalytic oxidation of aliphatic and aromatic sulfides to sulfoxides (90-95percent) using a buffered potassium peroxymonosulfate (Oxone) generated N-sulfonyloxaziridine is described.This oxidizing system is rapid and relatively intensitive to the reaction parameters and the structure of the sulfide.
- Davis, Franklin A.,Lal, Sankar G.,Durst, H. Dupont
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- Hybrid catalysts of molybdovanadophosphoric acid and g-C3N4with tunable bandgaps
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The integration of semiconductors and polyoxometalates provides promising benefits for the rational tuning of hybrid materials' electronic band structures; however, the intrinsic influence of certain hybridization approaches on the resulting bandgaps of their complexes has seldom been noted. Herein, graphitic carbon nitride and a series of phosphovanadomolybdates (H3+xPMo12-xVxO40, x = 0-3) have been complexed through electrostatic charge attraction, and their optical and electronic properties are fully explored to investigate the effect of minor variations of the polyoxometalate structures on the hybrid bandgaps and electronic structures. The conduction band edge of the hybrids increases along with the expansion of the number of vanadium centers in the phosphovanadomolybdate, providing potential guidance for the design of hybrid catalysts. This journal is
- Cai, Linkun,Hu, Jie,Li, Mu,Yin, Panchao
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- Keggin-type polyacid clusters on apatite: Characteristic catalytic activities in solvent-free oxidation
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We found that Keggin-type phosphometalates are effective catalysts for solvent-free oxidation with urea-H2O2 by dispersing on fluorapatite solid phase. In the solid phase system the phosphomolybdate (NH4)3PMo12O40 was more effective than the phosphotungstate (NH4)3PW12O40, whereas the latter was much superior to the former in the liquid-phase reaction with aqueous H2O2. In situ formation of novel peroxo-type species from (NH4)3PMo12O40/FAp and urea-H2O2, which may lead to the high catalytic activity in the solid phase system, was observed by 31P solid-state NMR.
- Ichihara, Junko,Yamaguchi, Shunro,Nomoto, Takuya,Nakayama, Hirokazu,Iteya, Katsuma,Naitoh, Nozomu,Sasaki, Yoh
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- Organophosphonate-Functionalized Lanthanopolyoxomolybdate: Synthesis, Characterization, Magnetism, Luminescence, and Catalysis of H2O2-Based Thioether Oxidation
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A novel class of organophosphonate-based polyoxomolybdate derivatives, K4H5[Ln3(H2O)14{(Mo8O24)(O3PCH2COO)3}2]·23H2O (Ln = Gd (1Gd), Tb (2Tb), Dy (3Dy)), have been fully investigated by a few characterization methods such as single-crystal X-ray crystallography, XRPD, elemental analysis, TGA, and IR spectra. The magnetic properties of 1Gd, 2Tb, and 3Dy were investigated, as well as the solid-state luminescence properties of 2Tb and 3Dy. The catalysis properties of 1Gd, 2Tb, and 3Dy for thioether oxidization have been investigated using hydrogen peroxide (H2O2) as an oxidant. The catalysis study demonstrated the efficient and selective conversion of various thioethers to their corresponding sulfones in excellent yields.
- Wang, Jiawei,Niu, Yanjun,Zhang, Meng,Ma, Pengtao,Zhang, Chao,Niu, Jingyang,Wang, Jingping
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- Synthesis and characterization of a Sb(v)-containing polyoxomolybdate serving as a catalyst for sulfoxidation
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A Sb-containing Anderson-based polyoxomolybdate cluster, [(CH3)4N]4H8[Na5Sb3(Sb2Mo12O57)]·17H2O [1; (CH3)4N+ = TMA+], has been successfully synthesized by using an aqueous solution method and structurally characterized. In particular, UV-Vis spectroscopy has been employed to elucidate the stability of the polyoxoanions. Under mild conditions, the catalyst demonstrates high activity and selectivity for the sulfoxidation of various sulfides in the presence of hydrogen peroxide. For example, thioanisole undergoes up to 100% conversion and 100% sulfone selectivity at 25 °C in aqueous solution.
- Lu, Jingkun,Wang, Yaping,Ma, Xinyi,Niu, Yanjun,Singh, Vikram,Ma, Pengtao,Zhang, Chao,Niu, Jingyang,Wang, Jingping
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- Spontaneous stepwise self-assembly of a polyoxometalate-organic hybrid into catalytically active one-dimensional anisotropic structures
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An inorganic-organic hybrid surfactant with a hexavanadate cluster as the polar head group was designed and observed to assemble into micelle structures, which further spontaneously coagulate into a 1D anisotropic structure in aqueous solutions. Such a hierarchical self-assembly process is driven by the cooperation of varied noncovalent interactions, including hydrophobic, electrostatic, and hydrogen-bonding interactions. The hydrophobic interaction drives the quick formation of the micelle structure; electrostatic interactions involving counterions leads to the further coagulation of the micelles into larger assemblies. This process is similar to the crystallization process, but the specific counterions and the directional hydrogen bonding lead to the 1D growth of the final assemblies. Since most of the hexavanadates are exposed to the surface, the 1D assembly with nanoscale thickness is a highly efficient heterogeneous catalyst for the oxidation of organic sulfides with appreciable recyclability. Surfing hybrids: Inorganic-organic hybrid surfactant with hexavanadate as the polar head group was programmed to assemble into a 1D structure with the cooperation of hydrophobic, electrostatic, and hydrogen-bonding interactions (see figure); these last interactions are directional and lead to the anisotropic assemblies. The nanobelts were highly efficient heterogeneous catalysts for oxidation of organic sulfides because most of the hexavanadates are exposed onto the surface.
- Yin, Panchao,Bayaguud, Aruuhan,Cheng, Peng,Haso, Fadi,Hu, Lang,Wang, Joy,Vezenov, Dmitri,Winans, Randall E.,Hao, Jian,Li, Tao,Wei, Yongge,Liu, Tianbo
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- Optically active polyoxometalate-based silica nanohelices: Induced chirality from inorganic nanohelices to achiral POM clusters
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In order to investigate the principle of chiral induction from nanometric silica helices to polyoxometalate (POM) clusters, a series of optically active silica POM-based nanohelices (NANOPOMs) have been prepared by electrostatic grafting and direct adsorption of a-Keggin polyoxometalate [a-PW12 O40]3 to well-defined left-and right-handed silica nanohelices. UV/Vis, Raman, DRIFT, TEM, HR-TEM, EDS and circular dichroism (CD) spectroscopy were used to characterize these NANOPOMs, and confirm the presence of POM clusters as well as their interactions with the helical support. The optical activity of the left-handed and right-handed NANOPOMs has been proven by CD spectroscopy. Their CD spectra are mirror images of one another, showing cotton effects at around 214 and 276 nm, this last contribution corresponding to the oxygen-to-tungsten charge-transfer bands of Keggin polyoxoanions. The CD signal of POM clusters is strongly enhanced for NANOPOMs built by adsorption of POM onto silica nanohelices, indicating a better induced optical activity to POM clusters. These nanohelices are stable, recoverable and active catalysts in the oxidation of sulfides. To the best of our knowledge, the present research represents the first examples of optically active POM-containing silica nanohelices in which achiral POM clusters have been grafted onto silica nanohelices, and display chiroptical effects.
- Attoui, Mariam,Pouget, Emilie,Oda, Reiko,Talaga, David,Bourdon, Gwéna Lle Le,Buffeteau, Thierry,Nlate, Sylvain
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- A Crown-Shaped Ru-Substituted Arsenotungstate for Selective Oxidation of Sulfides with Hydrogen Peroxide
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An acetate-bridged Ru-substituted arsenotungstate [H2N(CH3)2]14[As4W40O140{Ru2(CH3COO)}2]?22 H2O (1) has been synthesized and structurally characterized. Four Ru atoms occupy the respective lacunary S2 sites of the crown-shaped polyanion [As4W40O140]28?, and each Ru atom is coordinated by one As atom and five μ2-O atoms, comprising four from the S2 site and one from the acetate ligand. To the best of our knowledge, this coordination of the Ru atom, with an Ru?As bond length of 2.377(3)–2.387(3) ?, is unprecedented in polyoxometalate (POM) chemistry. Notably, 1 exhibits high efficiency, excellent selectivity, and good recyclability for the oxidation of sulfides with hydrogen peroxide (H2O2). Catalytic oxidation of various sulfides in the presence of 1 gives superior conversion and selectivity for sulfones in acetonitrile, whereas sulfoxides are obtained in methanol.
- Han, Mengdan,Niu, Yanjun,Wan, Rong,Xu, Qiaofei,Lu, Jingkun,Ma, Pengtao,Zhang, Chao,Niu, Jingyang,Wang, Jingping
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- Using Data Science To Guide Aryl Bromide Substrate Scope Analysis in a Ni/Photoredox-Catalyzed Cross-Coupling with Acetals as Alcohol-Derived Radical Sources
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Ni/photoredox catalysis has emerged as a powerful platform for C(sp2)–C(sp3) bond formation. While many of these methods typically employ aryl bromides as the C(sp2) coupling partner, a variety of aliphatic radical sources have been investigated. In principle, these reactions enable access to the same product scaffolds, but it can be hard to discern which method to employ because nonstandardized sets of aryl bromides are used in scope evaluation. Herein, we report a Ni/photoredox-catalyzed (deutero)methylation and alkylation of aryl halides where benzaldehyde di(alkyl) acetals serve as alcohol-derived radical sources. Reaction development, mechanistic studies, and late-stage derivatization of a biologically relevant aryl chloride, fenofibrate, are presented. Then, we describe the integration of data science techniques, including DFT featurization, dimensionality reduction, and hierarchical clustering, to delineate a diverse and succinct collection of aryl bromides that is representative of the chemical space of the substrate class. By superimposing scope examples from published Ni/photoredox methods on this same chemical space, we identify areas of sparse coverage and high versus low average yields, enabling comparisons between prior art and this new method. Additionally, we demonstrate that the systematically selected scope of aryl bromides can be used to quantify population-wide reactivity trends and reveal sources of possible functional group incompatibility with supervised machine learning.
- Doyle, Abigail G.,Gandhi, Shivaani S.,Jiang, Shutian,Kariofillis, Stavros K.,Martinez Alvarado, Jesus I.,?urański, Andrzej M.
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supporting information
p. 1045 - 1055
(2022/01/19)
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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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- Niobium(V) oxido tris-carbamate as easily available and robust catalytic precursor for the selective sulfide to sulfone oxidation
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The oxidation of the sulfide function promoted by a variety of vanadium compounds has been largely explored, whereas the use of homogeneous catalytic systems based on the heavier group 5 metals remains less explored. We report the use of easily available niobium and tantalum carbamates, i.e. [M(O2CNMe2)5] (M = Nb, 1; M = Ta, 2), [Nb(O2CNMe2)4], 3, [NbO(O2CNEt2)3], 4, and [NbCl3(O2CNEt2)2], 5, as effective catalysts for the conversion of a series of alkyl aryl and aromatic sulfides into the corresponding sulfones. NMR investigations on the performant niobium catalyst 4 unexpectedly revealed the substantial stability of this compound in the protic catalytic environment, and a plausible catalytic cycle was obtained by DFT studies. The two active catalytic species, i.e. 4 and its minor mono-methoxide derivative, presumably interconvert to each other exploiting the versatile coordination of the carbamato ligand.
- Bresciani, Giulio,Ciancaleoni, Gianluca,Crucianelli, Marcello,Gemmiti, Mario,Marchetti, Fabio,Pampaloni, Guido
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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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- 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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- Organocatalytic sulfoxidation
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Treatment of a sulfide with a catalytic amount of a 1,3-diketone in the presence of silica sulfuric acid as a co-catalyst and hydrogen peroxide (50% aq) as the stoichiometric oxidant leads to the corresponding sulfoxide product. The reaction is effective for diaryl, aryl-alkyl and dialkyl sulfides and is tolerant of oxidisable and acid sensitive functional groups. Investigations have shown that the tris-peroxide 2, formed on reaction of pentane-2,4-dione with hydrogen peroxide under acidic reaction conditions, can oxidise two equivalents of sulfide using the exocyclic peroxide groups whereas the endocyclic peroxide remains intact. Calculations provide a mechanism consistent with experimental observations and suggest the reaction proceeds via an initial acid catalysed ring opening of a protonated tris-peroxide prior to oxygen transfer to a sulfur nucleophile.
- Davidson, Stuart C.,Gomes, Gabriel dos Passos,Kuhn, Leah R.,Alabugin, Igor V.,Kennedy, Alan R.,Tomkinson, Nicholas C.O.
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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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- 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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- Electrochemical Scalable Sulfoxidation of Sulfides with Molecular Oxygen and Water
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An efficient and chemoselective synthesis of sulfoxides through the electrooxidation of sulfides has been well developed. This protocol takes advantage of electricity as the terminal oxidant and of molecular oxygen and water as the oxygen atom sources. A variety of structurally diverse sulfoxide compounds are assembled in moderate to excellent yields. The scaled-up reactions at 6–20 mmol show the good practicability and application potential of this methodology. A possible free radical mechanism has been proposed to rationalize the reaction procedure.
- Cheng, Zhen,Gao, Xinglian,Yao, Lingling,Wei, Zhaoxin,Qin, Guohui,Zhang, Yonghong,Wang, Bin,Xia, Yu,Abdukader, Ablimit,Xue, Fei,Jin, Weiwei,Liu, Chenjiang
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p. 3743 - 3747
(2021/07/26)
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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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- 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
(2021/02/13)
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- Tetrameric Lanthanide-Substituted Silicotungstate {Ln8Si4W40} Nanoclusters: Synthesis, Structural Characterization, Electrochemistry, and Catalytic Application for Oxidation of Thioethers
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All the title nanoclusters 1–10 with the molecular formula [(Ln2SiW10O38)4(W3O8)(OH)4(H2O)2]26? [LnIII =Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6), Er (7), Tm (8), Yb (9), and Y (10)] have been synthesized and isolated as mixed sodium and potassium salts. These nanoclusters are characterized by various analytical techniques such as FT-IR, UV/Vis, Photoluminescence, Single crystal X-ray diffraction, Electrochemistry, ICP-AES and Thermogravimetric analysis, and Powder X-ray diffraction. The {Ln8Si4W40} complexes show high efficiency and selectivity for the oxidation of thioethers using H2O2 as green oxidant. It is worth mentioning that the catalyst can be recovered even after five cycles of reaction with only a slight loss in its activity.
- Khan, Imran,Das, Vivek,Teillout, Anne-Lucie,Mbomekallé, Isra?l-Martyr,de Oliveira, Pedro,Sahoo, Subash Chandra,Hussain, Firasat
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supporting information
p. 1071 - 1081
(2021/03/16)
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- Single-Molecule Magnetic, Catalytic and Photoluminescence Properties of Heterometallic 3d–4f [Ln{PZn2W10O38(H2O)2}2]11? Tungstophosphate Nanoclusters
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A series of eleven lanthanide containing di-Zinc (II) substituted heterometallic 3d–4f sandwich-type tungstophosphate nanoclusters [Ln{PZn2W10O38(H2O)2}2]11? (Ln=NdIII, SmIII, EuIII, GdIII, TbIII, DyIII, HoIII, ErIII, TmIII, YbIII, and LuIII) have been synthesized by a single step reaction procedure. These clusters were characterized by various analytical techniques such as single crystal X-ray diffraction (SC-XRD), fourier transform infrared (FT-IR) spectroscopy, high-resolution electro-spray ionization mass spectrometry (HR-ESI-MS), inductively coupled plasma atomic emission spectroscopy (ICP-AES), solid UV/Vis, photoluminescence spectroscopy, powder X-ray diffraction (P-XRD) and thermogravimetric analysis (TGA). All the polyanions are isostructural and consists of a lanthanide ion sandwiched between two units of (1,5) isomer of di-Zn substituted α-Keggin type tungstophosphate. The complexes Sm-2 a, Eu-3 a, Tb-5 a, and Dy-6 a show good photoluminescence behavior. The catalytic properties were examined for the oxidation of thioethers. The catalyst is stable with a high turn over frequency (TOF) of 6250 h?1 and can be recovered even after 5 consecutive cycles. Furthermore, magnetic properties revealed that Gd-4 a, Tb-5 a, Dy-6 a, Er-8 a, and Yb-10 a show single-molecule magnetic properties.
- Das, Vivek,Khan, Imran,Hussain, Firasat,Sadakane, Masahiro,Tsunoji, Nao,Ichihashi, Katsuya,Kato, Chisato,Inoue, Katsuya,Nishihara, Sadafumi
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p. 3819 - 3831
(2021/09/22)
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- Selective synthesis of sulfoxides and sulfonesviacontrollable oxidation of sulfides withN-fluorobenzenesulfonimide
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A practical and mild method for the switchable synthesis of sulfoxides or sulfonesviaselective oxidation of sulfides using cheapN-fluorobenzenesulfonimide (NFSI) as the oxidant has been developed. These highly chemoselective transformations were simply achieved by varying the NFSI loading with H2O as the green solvent and oxygen source without any additives. The good functional group tolerance makes the strategy valuable.
- Cao, Zhong-Yan,Li, Xiaolong,Lu, Hao,Wang, Panpan,Wang, Shengqiang,Xu, Xiaobo,Yan, Leyu,Yang, A-Xiu
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supporting information
p. 8691 - 8695
(2021/10/22)
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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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- 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; 0019
(2021/02/24)
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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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- 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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- Multicomponent Reductive Cross-Coupling of an Inorganic Sulfur Dioxide Surrogate: Straightforward Construction of Diversely Functionalized Sulfones
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Conventionally, sulfones are prepared by oxidation of sulfides with strong oxidants. Now, a multicomponent reductive cross-coupling involving an inorganic salt (sodium metabisulfite) for the straightforward construction of sulfones is disclosed. Both intramolecular and intermolecular reductive cross-couplings were comprehensively explored, and diverse sulfones were accessible from the corresponding alkyl and aryl halides. Intramolecular cyclic sulfones were systematically obtained from five- to twelve-membered rings. Naturally occurring aliphatic systems, such as steroids, saccharides, and amino acids, were highly compatible with the SO2-insertion reductive cross-coupling. Four clinically applied drug molecules, which include multiple heteroatoms and functional groups with active hydrogens, were successfully prepared via a late-stage SO2 insertion. Mechanistic studies show that alkyl radicals and sulfonyl radicals were both involved as intermediates in this transformation.
- Meng, Yingying,Wang, Ming,Jiang, Xuefeng
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supporting information
p. 1346 - 1353
(2019/12/11)
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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 0040-0044
(2020/01/25)
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- Continuous bioinspired oxidation of sulfides
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A simple, efficient, and selective oxidation under flow conditions of sulfides into their corresponding sulfoxides and sulfones is reported herein, using as a catalyst perselenic acid generated in situ by the oxidation of selenium (IV) oxide in a diluted aqueous solution of hydrogen peroxide as the final oxidant. The scope of the proposed methodology was investigated using aryl alkyl sulfides, aryl vinyl sulfides, and dialkyl sulfides as substrates, evidencing, in general, a good applicability. The scaled-up synthesis of (methylsulfonyl)benzene was also demonstrated, leading to its gram-scale preparation.
- Crociani, Letizia,Mangiavacchi, Francesca,Marini, Francesca,Sancineto, Luca,Santi, Claudio
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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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- 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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- 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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- 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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- Genome Mining of Oxidation Modules in trans-Acyltransferase Polyketide Synthases Reveals a Culturable Source for Lobatamides
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Bacterial trans-acyltransferase polyketide synthases (trans-AT PKSs) are multimodular megaenzymes that biosynthesize many bioactive natural products. They contain a remarkable range of domains and module types that introduce different substituents into growing polyketide chains. As one such modification, we recently reported Baeyer–Villiger-type oxygen insertion into nascent polyketide backbones, thereby generating malonyl thioester intermediates. In this work, genome mining focusing on architecturally diverse oxidation modules in trans-AT PKSs led us to the culturable plant symbiont Gynuella sunshinyii, which harbors two distinct modules in one orphan PKS. The PKS product was revealed to be lobatamide A, a potent cytotoxin previously only known from a marine tunicate. Biochemical studies show that one module generates glycolyl thioester intermediates, while the other is proposed to be involved in oxime formation. The data suggest varied roles of oxygenation modules in the biosynthesis of polyketide scaffolds and support the importance of trans-AT PKSs in the specialized metabolism of symbiotic bacteria.
- Ueoka, Reiko,Meoded, Roy A.,Gran-Scheuch, Alejandro,Bhushan, Agneya,Fraaije, Marco W.,Piel, J?rn
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supporting information
p. 7761 - 7765
(2020/03/25)
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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 of Na22[((RE)4(H2O)6Sb6O4)(SbW10O37)2(SbW8O31)2] [(RE)III = Y, Gd, Tb, Dy, Ho, Er, Tm, Yb]: Synthesis, characterization and catalytic application
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A series of eight rare-earth substituted antimony tungstates with the formulae [((RE)4(H2O)6Sb6O4)(SbW10O37)2(SbW8O31)2]22– [(RE)III = Y(1), Gd(2), Tb(3), Dy(4), Ho(5), Er(6), Tm(7), Yb(8)] has been synthesized under ambient conditions. The compounds were isolated using rare-earth salts and Na9[B-α-SbW9O33]?19.5 H2O as precursors along with sodium dihydrogen phosphate in 1 M NaCl solution. The addition of dihydrogen phosphate was found to be a crucial step for the isolation of these polyanions. The polyanions were characterized by various analytical techniques such as single crystal X-ray diffraction (1a – 6a) (SC-XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA). The compounds were found to show efficient heterogeneous catalytic activity for oxidation of thioethers.
- Gupta, Rakesh,Hussain, Firasat,Kaushik, Reetam,Khan, Imran
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- Method for synthesizing organic sulfone molecules by using novel sulfone methylation reagent
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The invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing organic sulfone molecules by using a novel sulfone methylation reagent. According to the method, dimethyl phosphite is used as a novel sulfone methylation reagent, sulfonyl hydrazine is used as an initial reaction raw material, N,N-dimethyl formamide (DMF) is used as a reactionmedium, tetrabutyl ammonium iodide (Bu4NI) is used as a phase transfer catalyst, and the organic sulfone molecules are synthesized through a reaction at 60 DEG C. The method has the advantages that the raw materials are cheap and easily available, the method can be amplified to gram-level reaction to synthesize active organic sulfone molecules with a sulfone methyl structure, complex reaction conditions such as transition metal catalysts are not needed in the reaction, and heavy metal residues generated in synthesis of active drug molecules and pollution to the environment are avoided.
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Paragraph 0012; 0013
(2020/09/30)
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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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- 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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- Aryl alkyl sulfone compound and reducing coupling method for constructing sulfone compounds
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The invention discloses an aryl alkyl sulfone compound shown as a formula (1) and a synthetic method thereof. The aryl alkyl sulfone compound is prepared by taking an aromatic iodide, an inorganic sulfur reagent and an alkyl bromide as reaction raw materials to carry out reacting in a solvent under action of alkali, a catalyst, a ligand, a reducing agent and an additive. According to the invention, an inorganic sulfur reagent is used as a sulfur source to construct the aryl alkyl sulfone compound in one step under catalysis and reduction conditions, so that the defect in synthesizing the arylalkyl sulfone compound by conventional oxidation of thioether is avoided. The aryl alkyl sulfone compound developed by the invention can be used for synthesizing aryl alkyl sulfone medicines.
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Paragraph 0142-0146
(2019/12/25)
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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 0291-0292
(2019/05/15)
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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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- Electrochemical oxidations of thioethers: Modulation of oxidation potential using a hydrogen bonding network
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A highly efficient chemo-selective electrochemical oxidation of thioethers to sulfoxides and sulfones was developed. The hydrogen bonding network generated from hexafluoro-2-propanol (HFIP) and acetic acid (AcOH) plays an important role in the modulation of oxidation potential. The hydrogen bonding network complexes strongly with the sulfoxide, making it less prone to further oxidation. Therefore, thioethers can be selectively electrochemically oxidized to sulfoxides and over-oxidization could be minimized. Moreover, this modulation of oxidization via hydrogen bonding was supported by density functional theory (DFT) calculations and cyclic voltammetry experiments.
- Liu, Shiwen,Chen, Bocheng,Yang, Yi,Yang, Yuhao,Chen, Qianjin,Zeng, Xiaojun,Xu, Bo
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- Carbon nanotube-ruthenium hybrid towards mild oxidation of sulfides to sulfones: Efficient synthesis of diverse sulfonyl compounds
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A heterogeneous catalyst was assembled with ruthenium nanoparticles on carbon nanotubes and used in a mild oxidation method to prepare sulfones from sulfides. The system proved very efficient on the investigated substrates and the products were obtained in high yields.
- Almeida, Renata G.,De Carvalho, Renato L.,Nunes, Mateus P.,Gomes, Roberto S.,Pedrosa, Leandro F.,De Simone, Carlos A.,Gopi, Elumalai,Geertsen, Valérie,Gravel, Edmond,Doris, Eric,Da Silva Júnior, Eufranio N.
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p. 2742 - 2748
(2019/06/17)
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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 0120-0123
(2019/02/13)
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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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- Method for preparing sulfone by catalyzing sulfur oxide ether
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The invention belongs to the technical field of sulfone compound synthesis, and particularly relates to a method for preparing sulfone by catalyzing sulfur oxide ether. The method for preparing the sulfone by catalyzing the sulfur oxide ether specifically includes the steps that a catalyst, sulfur ether and a H2O2 solution with a mass fraction of 30% are mixed in a reaction bottle, and stirred for3-6 h at the room temperature to obtain the sulfone; the molar ratio of the catalyst to the sulfur ether to the H2O2 is 1:10000:50000; and the catalyst is prepared by the steps that a NaVO3 solutionis added to a hydrochloric acid solution of K8[SiW10O36].12H2O and stirred for 5 min to obtain a bright yellow filtrate before filtering, a chloroform solution of a compound A is added to the bright yellow filtrate drop by drop, continuously stirred for 5 h to collect solid, and the solid is the catalyst. According to the method for preparing the sulfone by catalyzing the sulfur oxide ether, the used catalyst has a high conversion number, an organic solvent does not need to be used in the reaction process, and the sulfone can be prepared at the room temperature.
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Paragraph 0028; 0035; 0036
(2020/01/03)
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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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- Efficient Liquid-Assisted Grinding Selective Aqueous Oxidation of Sulfides Using Supported Heteropolyacid Catalysts
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The present work reports the preparation of 40MoAl200 and its full characterization using a number of analytical techniques (XRD, TEM, TGA, BET, EDX). Liquid-assisted ball milling proved to be a key tool to achieve both the best efficiency of 40MoAl200 as a novel Keggin type catalyst in the selective sulfoxidation reaction and also for succeeding in its effective recovery and reuse. In addition, the liquid assisted grinding process was studied in detail evaluating the influence of different parameters such as frequency of rotation (rpm), number and size of the stainless steel balls used and reaction time. The use of aqueous hydrogen peroxide is essential as water proved to exert a crucial role to improve both yields and selectivity towards sulfoxide formation. The procedure was representatively extended to a number of substrates with the possibility to extend the scope of the system to produce sulfoxides in high yields (up to 95 %) and satisfactory selectivities (up to 80 %). The catalyst proved to be recoverable and reusable under the optimized reaction conditions.
- Trombettoni, Valeria,Franco, Ana,Sathicq, A. Gabriel,Len, Christophe,Romanelli, Gustavo P.,Vaccaro, Luigi,Luque, Rafael
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p. 2537 - 2545
(2019/04/30)
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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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- A versatile and recyclable molecularly imprinted polymer as an oxidative catalyst of sulfur derivatives: A new possible method for mustard gas and v nerve agent decontamination
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A molecularly imprinted polymer containing a porphyrin unit was developed as a biomimetic heterogenous catalyst for the oxidation of sulfur derivatives. Its catalytic efficiency under mild conditions and its easy recovery represent a great asset for the design of new decontamination tools for yperite and VX.
- Mohamed, Sophie,Balieu, Sébastien,Petit, Emilie,Galas, Ludovic,Schapman, Damien,Hardouin, Julie,Baati, Rachid,Estour, Fran?ois
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supporting information
p. 13243 - 13246
(2019/11/16)
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- SYNTHESIS OF MESOTRIONE
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The present disclosure relates to a method for the synthesis of mesotrione. The method comprises reacting p-toluene sulfonyl chloride with alkali metal sulphite and alkali metal bicarbonate to obtain p-toluene alkali metal sulfinate. The p-toluene alkali metal sulfinate is reacted with alkali metal salt of monochloroacetic acid to obtain p- methylsulfonyl toluene. Further, p-methylsulfonyl toluene is nitrated to obtain 2-nitro-p- methylsulfonyl toluene. 2-nitro-p-methylsulfonyl toluene is oxidized and then halogenated to obtain 2-nitro-p-methylsulfonylbenzoyl halide. 2-nitro-p-methylsulfonylbenzoyl halide is reacted with alkali metal salt of 1,3-cyclohexanedione to obtain 3-(2-Nitro-p-methyl sulfonyl benzoyloxy) cyclohexane-l-one. 3-(2-Nitro-p-methyl sulfonyl benzoyloxy) cyclohexane-1- one is reacted with base, a third fluid medium and cyanide ion source to obtain an amorphous mesotrione. The present disclosure also discloses the steps of converting the amorphous mesotrione to crystalline mesotrione having purity greater than 99 %. The process of the present disclosure for preparing mesotrione is rapid, economic, and environment friendly.
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Page/Page column 14; 15
(2018/10/25)
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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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