- 3-(4-Hydroxymethylphenylsulfanyl)propanoic acid (HMPPA) as a new safety catch linker in solid phase peptide synthesis
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A new safety catch linker, 3-(4-hydroxymethylphenylsulfanyl)propanoic acid (HMPPA), is described for use in solid phase peptide synthesis. The linker is readily synthesized from commercially available chemicals in a more cost efficient way compared to similar reported linkers. The HMPPA linker is easily attached to an amino derivatized solid support followed by on-resin oxidation of the thioether to sulfoxide, thereby making the linker very stable towards strong acid treatment. Final resin cleavage is performed by reductive acidolysis.
- Erlandsson, Mikael,Undén, Anders
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Read Online
- 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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- Flow Electrosynthesis of Sulfoxides, Sulfones, and Sulfoximines without Supporting Electrolytes
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An efficient electrochemical flow process for the selective oxidation of sulfides to sulfoxides and sulfones and of sulfoxides toN-cyanosulfoximines has been developed. In total, 69 examples of sulfoxides, sulfones, andN-cyanosulfoximines have been synthesized in good to excellent yields and with high current efficiencies. The synthesis was assisted and facilitated through a supporting electrolyte-free, fully automated electrochemical protocol that highlights the advantages of flow electrolysis.
- Amri, Nasser,Wirth, Thomas
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p. 15961 - 15972
(2021/07/20)
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- COMPOSITES, METHODS AND USES THEREOF
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The present invention relates, in general terms, to methods of catalysing a reaction, including the steps of contacting a chemical entity comprising a sulphide moiety with a composite and an oxidant. The composite acts as a heterogeneous catalyst to oxidise the sulphide moiety. The present invention also relates to composites, methods of synthesising the composites and its use as a catalyst thereof.
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Page/Page column 28
(2021/06/04)
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- Synthesis of an anthraquinone-containing polymeric photosensitizer and its application in aerobic photooxidation of thioethers
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Work on the synthesis of a polymeric photosensitizer and its application in the photooxidation of thioethers is reported herein. Firstly, the polymeric photosensitizer was designed and synthesized by the reaction of anthraquinone-2-carbonyl chloride (AQ-2-COCl) with poly(2-hydroxyethyl methacrylate) (PHEMA). Then, the visible light-induced photooxidation of thioethers under aerobic conditions was investigated. The results revealed that the reaction yielded sulfoxides highly chemoselectively in excellent yields with good substrate tolerance. Importantly, AQ-PHEMA could be easily recovered and reused more than 20 times without significant loss of the catalytic activity.
- Chen, Yang,Ding, Aishun,Hu, Jianhua
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p. 10661 - 10665
(2020/03/27)
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- Cobalt Single-Atom-Intercalated Molybdenum Disulfide for Sulfide Oxidation with Exceptional Chemoselectivity
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The identification of chemoselective oxidation process en route to fine chemicals and specialty chemicals is a long-standing pursuit in chemical synthesis. A vertically structured, cobalt single atom-intercalated molybdenum disulfide catalyst (Co1-in-MoS2) is developed for the chemoselective transformation of sulfides to sulfone derivatives. The single-atom encapsulation alters the electron structure of catalyst owing to confinement effect and strong metal–substrate interaction, thus enhancing adsorption of sulfides and chemoselective oxidation at the edge sites of MoS2 to achieve excellent yields of up to 99% for 34 examples. The synthetic scopes can be extended to sulfide-bearing alkenes, alkynes, aldehydes, ketones, boronic esters, and amines derivatives as a toolbox for the synthesis of high-value, multifunctional sulfones and late-stage functionalization of pharmaceuticals, e.g., Tamiflu. The synthetic utility of cobalt single atom-intercalated MoS2, together with its reusability, scalability, and simplified purification process, renders it promising for industrial productions.
- Chen, Zhongxin,Liu, Cuibo,Liu, Jia,Li, Jing,Xi, Shibo,Chi, Xiao,Xu, Haisen,Park, In-Hyeok,Peng, Xinwen,Li, Xing,Yu, Wei,Liu, Xiaowang,Zhong, Linxin,Leng, Kai,Huang, Wei,Koh, Ming Joo,Loh, Kian Ping
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- Development of a simple high-throughput assay for directed evolution of enantioselective sulfoxide reductases
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We report on the development of high-throughput fluorogenic assay that can streamline directed evolution of enantioselective sulfoxide reductases. As a model, methionine sulfoxide reductase A (MsrA) has been evolved to expand its limited substrate scope. The resulting mutant MsrA can resolve a range of new challenging racemic sulfoxides with high efficiency including the pharmaceutically relevant albendazole sulfoxide. The simplicity and the level of throughput make this method also suitable for the screening of metagenomic libraries in future for the discovery of new enzymes with similar reactivities.
- Tarallo, Vincenzo,Sudarshan, Kasireddy,Nosek, Vladimír,Mí?ek, Jirí
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supporting information
p. 5386 - 5388
(2020/06/04)
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- B2cat2-Mediated Reduction of Sulfoxides to Sulfides
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An efficient and operationally simple method for the reduction of sulfoxides to sulfides has been developed using bis(catecholato)diboron (B2cat2) as a reducing agent. The present method accommodates various functional groups which are generally prone to reduction: halides, alkynes, carbonyls, nitriles, and heterocycles are totally intact, and only sulfoxide moieties undergo reduction chemoselectively. Moreover, the remaining diboron and the resulting boron-containing wastes are readily removable, the practicality of this protocol being thus demonstrated.
- Takahashi, Fumiya,Nogi, Keisuke,Yorimitsu, Hideki
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supporting information
p. 3009 - 3012
(2020/03/25)
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- Polymer-supported eosin Y as a reusable photocatalyst for visible light mediated organic transformations
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A novel polymer-supported recyclable photocatalyst has been developed for visible light mediated oxidation reactions. The organic dye eosin Y was loaded on macroporous commercially available Amberlite IRA 900 chloride resin and exploited as a photocatalyst for visible light mediated oxidation of thioethers to sulfoxides and phenylboronic acids to phenols under open atmospheric air. Varieties of functional groups were well tolerated during oxidation. The catalyst is recyclable for six cycles without significant loss in its efficiency. Furthermore, gram-scale oxidation of sulfides to sulfoxides has been demonstrated to prove the commercial viability of the method.
- Sridhar, Arunasalam,Rangasamy, Rajmohan,Selvaraj, Mari
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p. 17974 - 17979
(2019/12/02)
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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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- Method for preparing methylsulfonyl benzaldehyde without catalyst
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The invention relates to a novel method for preparing methylsulfonyl benzaldehyde without a catalyst. The method comprises the following steps: taking isobutyraldehyde as a coreduction agent, taking oxygen as an oxidizing agent, and directly oxidizing methylthio benzaldehyde, thereby obtaining the corresponding sulfone. Under the condition that the ratio of n(isobutyraldehyde) to n(methylthio benzaldehyde) is 3.5:1, acetonitrile is selected as a solvent, a reaction is carried out for 40 minutes, the amount of the methylthio benzaldehyde is 1.25*10 mol, the reaction is carried out at a temperature of 50 DEG C and the oxygen flow is 40mL/min, the conversion rate of the methylthio benzaldehyde can reach 99.5%, and the selectivity can reach 98.9%. Compared with other catalytic oxidation methods, the method disclosed by the invention does not need a catalyst and is simple and convenient to operate.
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Paragraph 0012-0026
(2019/10/01)
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- Aluminum(III) Chloride Promoted Oxygen Transfer: Selective Oxidation of Sulfides to Sulfoxides
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An efficient selective oxidation of sulfides to sulfoxides has been developed by means of AlCl 3 -promoted oxygen transfer from phenyliodine diacetate [PhI(OAc) 2 ]. AlCl 3 proved to be the optimalLewis acid for the activation of PhI(OAc) 2. Various substituted sulfides were selectively transformed into the corresponding sulfoxides in good to excellent yields (≤99%). The high efficiency, excellent functional-group compatibility, broad substrate scope, and mild conditions render the current transformation useful for the synthesis of sulfoxides.
- Xie, Yongtao,Li, Yuxin,Zhou, Sha,Zhou, Shaa,Zhang, Yan,Chen, Minggui,Li, Zhengming
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supporting information
p. 340 - 343
(2017/12/06)
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- A novel catalytic system poly(1-vinyl-3-dodecylimidazolium tribromide)/TBN for the oxidation of sulfides to sulfoxides with air as oxidant
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A novel and recoverable polymeric ionic liquid, poly(1-vinyl-3-dodecylimidazolium tribromide) (Poly[VDIM]Br3), was successfully prepared and fully characterized. And a highly efficient metal-free catalytic system Poly[VDIM]Br3/tert-butyl nitrite was developed for the oxidation of sulfides. With air as oxidant, we have successfully achieved 19 kinds of sulfides selectively and efficiently oxidized to corresponding sulfoxides using this catalytic system at room temperature.
- Zhang, Hua,Qi, Linlin
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p. 3171 - 3174
(2018/07/13)
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- The sulfoxidation reaction catalyzed by CoBr2 complexes, under the magnifying glass of green parameters
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Different cobalt (II) and nickel (II) species were used as catalysts in sulfoxidation reactions giving excellent yields and high chemoselectivity. Among the cobalt (II) species, both γ-cyclodextrin complexes synthesized in ethyl acetate or dichloromethane solvents were very good catalysts, while γCDNiBr2 synthesized in ethyl acetate was the best of Ni (II) species. Sulfoxidation takes place with high chemoselectivity in the presence of other groups such as aldehyde. Good results were obtained when these reactions were analyzed using green chemistry metrics. Techniques as FT-IR, UV–vis Diffuse Reflectance, colorimetry, TGA, flame atomic absorption, potentiometric halide titration, and elemental analysis were used to characterize novel complexes. The change of solvent in the synthesis of complexes produces positive effects in holistic green metrics.
- Pinilla Pe?a, Diana C.,Rossi, Laura I.
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- Selective Oxidation of Sulfides in Flow Chemistry
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A packed-bed reactor with oxone has been employed for selective oxidations of sulfur compounds. Various sulfides containing different functional groups are efficiently oxidized to the corresponding sulfoxides without formation of sulfones or other side products.
- Silva, Filipa,Baker, Alastair,Stansall, James,Michalska, Weronika,Yusubov, Mehkman S.,Graz, Michael,Saunders, Robert,Evans, Gareth J. S.,Wirth, Thomas
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supporting information
p. 2134 - 2137
(2018/05/31)
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- Selective oxidation method of thioether
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The invention relates to a selective oxidation method of thioether, and discloses a novel synthesis method of a single sulfone compound shown as a formula (I). According to the invention, thioether shown in a formula (II) is taken as a raw material, under existence of tert-butyl hydroperoxide, an oxidation reaction is carried out in a solvent, after the reaction is completed, and through post-treatment, the single sulfone compound shown as the formula (I) is obtained. Compared with the prior art, an oxidizing agent tert-butyl hydroperoxide which is friendly to environment is employed, usage ofa metal catalyst is avoided, the reaction condition is mild, selectivity is high, the operation is simple, the applicability is wide, and the reaction yield is high.
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Paragraph 0042; 0043; 0044
(2018/09/20)
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- Synthesis of: N -alkylated 2-pyridones through Pummerer type reactions of activated sulfoxides and 2-fluoropyridine derivatives
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N-Alkylated 2-pyridone products were obtained in good to excellent yields through a one-pot procedure involving either normal or interrupted Pummerer reactions between triflic anhydride activated sulfoxides and 2-fluoropyridine derivatives, followed by hydrolysis. This is a rare case that uses 2-fluoropyridine as a nucleophile in Pummerer type reactions.
- Hu, Gang,Xu, Jiaxi,Li, Pingfan
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p. 4151 - 4158
(2018/06/12)
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- Iron(III) Amine Bis(phenolate) Complex Immobilized on Silica-Coated Magnetic Nanoparticles: A Highly Efficient Catalyst for the Oxidation of Alcohols and Sulfides
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We aimed to immobilize a complex of iron(III) amine bis(phenolate) on silica-coated magnetic nanoparticles as a new magnetically recoverable catalyst (Fe3O4@SiO2-APTES-FeLGDC). Both the chemical nature and the structure of catalyst were confirmed by using field-emission transmission electron microscopy, field-emission scanning electron microscopy, FTIR spectroscopy, thermogravimetric analysis, vibrating sample magnetometry, X-ray photoelectron spectroscopy, XRD, atomic absorption spectroscopy, and elemental analysis. This sustainable catalyst leads to the efficient oxidation of a wide range of alcohols and sulfides with excellent conversion and selectivity under a mild conditions to their corresponding oxidized products, acids (or ketones) and sulfoxides, respectively. Furthermore, the stability of the structure and morphology of our efficient recyclable system was investigated, and all of the data proved that the complex was anchored firmly to the magnetite nanoparticles.
- Karimpour, Touraj,Safaei, Elham,Karimi, Babak,Lee, Yong-Ill
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p. 1889 - 1899
(2018/01/04)
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- Controlled Aerobic Oxidation of Primary Benzylic Alcohols to Aldehydes Catalyzed by Polymer-Supported Triazine-Based Dendrimer-Copper Composites
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A controlled aerobic oxidation of primary benzylic alcohols to the corresponding benzaldehydes by using polystyrene-poly(ethylene glycol) (PS-PEG) resin-supported triazine-based polyethyleneamine dendrimer-copper complexes [PS-PEG-TD2-Cu(II)] was developed. In particular, PS-PEG-TD2-Cu(OAc) 2 efficiently catalyzed the aerobic oxidation of benzylic alcohols in the presence of a catalytic amount of TEMPO under atmospheric conditions to give the corresponding aldehydes in up to quantitative yield. The catalyst was readily recovered by simple filtration and reused four times without significant loss of its catalytic activity.
- Pan, Shiguang,Yan, Shuo,Osako, Takao,Uozumi, Yasuhiro
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supporting information
p. 1152 - 1156
(2018/04/16)
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- Metal- and additive-free oxygen-atom transfer reaction: an efficient and chemoselective oxidation of sulfides to sulfoxides with cyclic diacyl peroxides
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Metal- and additive-free oxidation of a series of sulfides/thioketones has been achieved using cyclic diacyl peroxides as mild oxygen sources. This protocol features simple manipulation, high chemo- and diastereoselectivity, and a broad substrate scope (up to 42 examples), tolerates many common functional groups, and is scalable and applicable to the late-stage sulfoxidation strategy. A preliminary mechanistic study by quantum mechanical calculations suggests that a single two-electron transfer process is energetically more favorable, and indicates the reactivity of cyclic diacyl peroxides distinct from conventional acyclic acyl peroxides.
- Gan, Shaoyan,Yin, Junjie,Yao, Yuan,Liu, Yang,Chang, Denghu,Zhu, Dan,Shi, Lei
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supporting information
p. 2647 - 2654
(2017/04/03)
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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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- Access to N-cyanosulfoximines by transition metal-free iminations of sulfoxides
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A transition metal-free synthesis of N-cyanosulfoximines from sulfoxides using N-chlorosuccinimide (NCS) as oxidising agent and cyanamide as nucleophilic amine source is reported. The products are obtained in moderate to excellent yields. The protocol enables an easy access to N-cyanosulfoximines from readily available starting materials under inversion of configuration at a preexisting stereogenic center.
- Dannenberg,Fritze,Krauskopf,Bolm
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supporting information
p. 1086 - 1090
(2017/02/10)
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- Catalyst-free oxidation of sulfides to sulfoxides and diethylamine catalyzed oxidation of sulfides to sulfones using Oxone as an oxidant
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Abstract: We describe here our journey from the failure of our attempts in controlled oxidation of sulfides to sulfoxides using an Oxone–KBr combination to our success in the development of a catalyst-free protocol for the oxidation of sulfides to sulfoxides using Oxone as an oxidant. We also describe the failure of our attempts at the oxidation of sulfides to sulfones using an excess of Oxone–KBr as well as Oxone, and our success towards the development of a rapid, scalable and chromatography-free protocol for the oxidation of sulfides to sulfones using diethylamine–Oxone as an unprecedented catalyst–oxidant combination.
- Kupwade,Khot,Lad,Desai,Wadgaonkar
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p. 6875 - 6888
(2017/10/06)
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- A chemoselective oxidation of sulfides to sulfoxides and sulfones using urea-2,2-dihydroperoxypropane as a novel oxidant
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Background: Sulfoxides and sulfones have been in the center of attention due to their wide range of promises in various approaches. The functional groups presented in these compounds serve as important building blocks in numerous natural, pharmeceutical and agricultural compounds. These deriatives have been prepared through a multitude of routes which were accompanied by several drawbacks. Therefore, there has been an ever-increasing interest to find a new methodology that leads to the production of these compounds via an environmentally benign path bringing about high yields. Recently, gem-dihydroperoxides have attracted much attention due to their oxidizing power and they have been utilized in several oxidation processes. Methods: We carried out a chemoselective oxidation of sulfides to sulfoxides and sulfones on treatment with urea-2,2-dihydroperoxypropane, a solid oxidant composed of equal amounts of 2,2-dihydroperoxypropane and urea, using THF as the solvent under catalyst-free conditions at room temprature. Results: Sulfides possessing a variety of substitutions namely dialkyl, diaryl, ally l and alkyl-aryl were subjected to the optimized reaction conditions and they could successfully afford different amounts of sulfoxides and sulfones depending on the amount of the oxidant utilized. Based on the results, electron-donating groups accelerated the reaction while electron-withdrawing substituents lowered the reactivity. Conclusion: Urea-2,2-dihydroperoxypropane as a solid oxidant which can be stored for several months without any loss in its activity has proved its capability to oxidize sulfides to sulfoxides and sulfones under catalyst-free and mild conditions. This approach is a cost-effective and environmentally benign methodology via which the products have been synthesized in high yields and short reaction times.
- Khosravi, Kaveh,Naserifar, Shirin,Asgari, Atefeh
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p. 749 - 756
(2017/02/05)
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- SULFOXIDATION CATALYSTS AND METHODS FOR THEIR PREPARATION AND USE
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Methods and compositions of catalysts for sulfoxidation reaction processes are disclosed. The sulfoxidation reaction process can be performed in an aqueous medium, and the catalysts can be recycled for further use. In some embodiments, a method of making a catalyst may include contacting a transition metal compound with an oxidizing agent to form a first solution, contacting a carboxylic acid compound with a cationic surfactant to form a second solution, mixing the first solution and the second solution to form a precipitate, and isolating the precipitate.
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Paragraph 0054; 055
(2016/09/26)
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- An organic-inorganic hybrid supramolecular framework material based on a [P2W18O62]6- cluster and Yb & Na complexes of pyridine-2,6-dicarboxylic acid: A catalyst for selective oxidation of sulfides in water with H2O2
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A rare-earth-containing polyoxometalate (RECP) hybrid, {(Yb (PDCH2)2(PDCH))·Na(H2O)2·(Na(PDCH)(H2O)2)}2[P2W18O62]·14H2O (1), based on [P2W18O62]6- cluster anions and cationic Yb & Na complex units of pyridine-2,6-dicarboxylic acid (PDCH2) has been synthesized under normal reaction conditions, which exhibited a supramolecular 3-D framework structure in the crystal lattice. Hybrid 1 acts as a green catalyst for the selective oxidation of sulfides in water with H2O2 as the reagent.
- Reddy, Pulikanti Guruprasad,Mamidi, Narsimha,Pradeep, Chullikkattil P.
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p. 4272 - 4276
(2016/07/06)
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- Synthetic utility of iodic acid in the oxidation of benzylic alcohols to aromatic aldehydes and ketones
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Various primary and secondary benzylic alcohols were efficiently oxidized to aromatic aldehydes and aromatic ketones with iodic acid in DMF at 60?°C for 2?h and with iodic acid in the presence of TEMPO (5?mol?%) in DMF at room temperature, respectively. The former method was effective for the oxidation of sterically hindered alcohols at 60?°C and the latter method was effective for the oxidation of less sterically hindered alcohols at room temperature.
- Imai, Sho,Togo, Hideo
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p. 6948 - 6954
(2016/10/13)
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- Carbon-supported metal-modified lacunary tungstosilicic polyoxometallates used as catalysts in the selective oxidation of sulfides
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Lacunary tungstosilicic polyoxometallates modified with transition metal ions [SiW11O39M(H2O)]6-, where M = Mn2+, Fe2+, Co2+or Cu2+, were synthesized and supported on activated carbon to obtain the SiW11MC catalysts. The samples were characterized by FT-IR, XRD, N2 adsorption-desorption measurements, and the acidic properties were determined using the isopropanol dehydration test reaction. The activity and selectivity of the catalysts were evaluated in the selective oxidation of a series of sulfides to sulfoxides or sulfone. The reaction was carried out in acetonitrile as solvent using H2O2 35% p/V as a clean oxidant. The conversion values decreased in the following order: SiW11MnC > SiW11FeC > SiW11CuC > SiW11CoC. The catalysts were reused without appreciable loss of their catalytic activity. It was found that the activity of the catalysts decreases in parallel with the increment in the reduction temperature values. The most easily reducible catalyst displayed the highest conversion values. We found a convenient and selective procedure for oxidizing sulfides to sulfoxides or sulfones using aqueous hydrogen peroxide and a catalytic amount of lacunary tungstosilicic polyoxometallates supported on carbon at low temperatures (20-50 °C) in a reasonably short reaction time
- Frenzel, Romina,Sathicq, ángel G.,Blanco, Mirta N.,Romanelli, Gustavo P.,Pizzio, Luis R.
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- Polyoxomolybdate-Calix[4]arene Hybrid: A Catalyst for Sulfoxidation Reactions with Hydrogen Peroxide
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An easily accessible polyoxomolybdate-calix[4]arene hybrid 1 has been synthesized and applied as a heterogeneous catalyst in the sulfoxidation of thioethers to sulfoxides and to sulfones under strictly stoichiometric amounts of 30% H2O2 in CH3CN as the solvent. This study represents the first promising example of successful employment of calixarenes-polyoxometalate (POM) hybrid materials in the area of catalytic oxidations.
- Meninno, Sara,Parrella, Alessandro,Brancatelli, Giovanna,Geremia, Silvano,Gaeta, Carmine,Talotta, Carmen,Neri, Placido,Lattanzi, Alessandra
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supporting information
p. 5100 - 5103
(2015/11/03)
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- Selective synthesis of sulfoxides and sulfones from sulfides using silica bromide as the heterogeneous promoter and hydrogen peroxide as the terminal oxidant
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Silica bromide as a heterogeneous promoter and reagent is prepared from the reaction of silica gel with PBr3as a non-hydroscopic, filterable, cheap, and stable yellowish powder that can be stored for months. The results show that silica bromide is a suitable and efficient promoter for the chemoselective oxidation of sulfides to the corresponding sulfoxides or sulfones in the presence of 30% H2O2in acetonitrile. The excellent yields, heterogeneous conditions, simplicity, compatibility with a variety of functionalities, and ease of isolation of the products make our procedure a practical alternative.
- Maleki, Behrooz,Hemmati, Saba,Sedrpoushan, Alireza,Ashrafi, Samaneh Sedigh,Veisi, Hojat
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p. 40505 - 40510
(2015/02/03)
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- Nickel ferrite nanoparticles-hydrogen peroxide: A green catalyst-oxidant combination in chemoselective oxidation of thiols to disulfides and sulfides to sulfoxides
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Nickel ferrite nanoparticles-hydrogen peroxide has been demonstrated for the first time as a green and efficient catalyst-oxidant combination in the chemoselective oxidation of thiols to disulfides and sulfides to sulfoxides. This magnetically separable catalyst was found to be reusable for five consecutive runs without appreciable change in the activity, as well as composition of the catalyst. The mechanism for the oxidation of thiols and sulfides has also been proposed. the Partner Organisations 2014.
- Kulkarni, Aparna M.,Desai, Uday V.,Pandit, Kapil S.,Kulkarni, Makarand A.,Wadgaonkar, Prakash P.
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p. 36702 - 36707
(2014/12/10)
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- A molybdenum based metallomicellar catalyst for controlled and selective sulfoxidation reactions in aqueous medium
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A surfactant based molybdenum system that exhibits catalytic activity for sulfoxidation reactions of various organic sulfides in aqueous medium has been developed and comprehensively characterized using IR, XRD, NMR, ESI-MS, DLS and TEM. The catalyst showcases remarkable selectivity for the preparation of both sulfoxides and sulfones in the range of good to excellent yields. Furthermore, the catalyst showed a high degree of tolerance towards various sensitive functional groups such as hydroxyl, acetal, aldehyde, amine, imine, oxime, cyano and alkene. the Partner Organisations 2014.
- Chakravarthy, Rajan Deepan,Ramkumar, Venkatachalam,Chand, Dillip Kumar
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p. 2190 - 2196
(2014/04/17)
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- Selective Oxidation of Sulfides to Sulfoxides Using Modified Keggin Heteropolyacids as Catalyst
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The use of modified Keggin phosphomolybdic heteropolyacids (HPA) (V and Al) as catalysts in the selective oxidation of sulfides to the corresponding sulfoxides is reported. Excellent yields were obtained (13 examples: 79%-95%), using 35% (w/v) aqueous hydrogen peroxide as oxidant, and acetonitrile as solvent at 25°C. The relationship between the electron densities of the sulfur atoms, which was estimated by molecular theoretical calculations, and the oxidative relativities of the sulfur-containing compounds was also investigated. The results indicate that the time for 100% conversion decreases with an increase in electron density.
- Palermo, Valeria,Sathicq, Angel G.,Vazquez, Patricia G.,Romanelli, Gustavo P.
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supporting information
p. 1423 - 1432
(2015/10/29)
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- A general and selective zinc-catalyzed oxidation of sulfides to sulfoxides
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A general zinc-catalyzed oxidation of sulfides to sulfoxides has been developed. All the reactions proceeded at room temperature. Hydrogen peroxide was used as a green oxidant. Twenty-one examples of sulfoxides were prepared in moderate to excellent yields.
- Wu, Xiao-Feng
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experimental part
p. 4328 - 4331
(2012/09/22)
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- Keggin heteropolycompounds as catalysts for liquid-phase oxidation of sulfides to sulfoxides/sulfones by hydrogen peroxide
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H4PMo11VO40, H5PMo 10V2O40 and H9PMo6V 6O40 acids and an acidic pyridinium salt of H 4PMo11VO40 were synthesized. They were characterized by FT-IR and the variations of their acid properties were determined by titration with n-butylamine. They proved to be highly active and selective catalysts for the hydrogen peroxide oxidation of methyl phenyl sulfide to the corresponding sulfoxide or sulfone. The conversion and selectivity results may be explained in terms of the co-existence of acidic and oxidative properties in the catalysts. On the other hand, a convenient catalytic homogeneous procedure has been found to oxidize different sulfides to sulfoxides or sulfones, with 35% aqueous H2O2, using (PyH)H 3PMo11VO40 as catalyst. The oxidation reaction is carried out at room temperature for sulfoxides or 40 °C for sulfones and requires a short time. The sulfoxides or sulfones were obtained with excellent yields by controlling the amount of H2O2.
- Romanelli, Gustavo P.,Villabrille, Paula I.,Cáceres, Cármen V.,Vázquez, Patricia G.,Tundo, Pietro
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p. 726 - 730
(2013/01/09)
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- Mild and efficient deoxygenation of sulfoxides to sulfides with Cp 2TiCl2/gallium system
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The Cp2TiCl2/Ga system was found to be a new reagent for reducing a variety of sulfoxides to the corresponding sulfides in good to excellent yields under mild conditions. Copyright
- Yoo, Byung Woo,Min, Sang Ki
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body text
p. 2993 - 2996
(2011/09/14)
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- Development of new recyclable reagents and catalytic systems based on hypervalent iodine compounds
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Recent advances in the development of polymer-supported iodine(V) oxidants, recyclable monomeric hypervalent iodine(III) reagents and catalytic systems based on hypervalent iodine compounds are discussed. These efficient and environmentally friendly reagents and catalysts are particularly useful for oxidative transformations of alcohols to carbonyl compounds and for oxidations at the benzylic position.
- Yusubov, Mekhman S.,Zhdankin, Viktor V.
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experimental part
p. 185 - 191
(2011/03/19)
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- Preparation and reactivity of polystyrene-supported iodosylbenzene sulfate: An efficient recyclable oxidizing system
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A new polymer-supported hypervalent iodine reagent, polystyrene-supported iodosylbenzene sulfate (PS-IBS), can be conveniently prepared by the reaction of polystyrene-supported (diacetoxyiodo)benzene (PS-DIB) with sodium bisulfate monohydrate under solvent-free conditions. This new recyclable reagent effects clean and efficient oxidation of a wide range of alcohols and sulfides to the corresponding carbonyl compounds or sulfoxides in high conversions under mild conditions. The final products are conveniently separated from the polymeric byproduct by simple filtration and isolated in good purity after evaporation of solvent. Recycling of the resin is possible with minimal loss of activity after several reoxidations.
- Chen, Jiang-Min,Zeng, Xiao-Mei,Zhdankin, Viktor V.
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experimental part
p. 2771 - 2774
(2010/12/25)
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- Mechanism of the selective sulfide oxidation promoted by HNO 3/FeBr3
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(Chemical Equation Presented) The oxidation of aryl methyl sulfides containing electron withdrawing and electron donating groups (p-NO2, p-CHO, p-NCS, p-Br, H, p-CH3, p-OCH3) was carried out in homogeneous solution in acetonitrile in the presence of catalytic amounts of HNO3 and FeBr3. The FeBr3 is required for the reaction to proceed for compounds with strongly electron withdrawing groups (p-NO2 and p-CHO) but is not necessary in the case of all the other compounds, although in the latter cases the yield decreases considerably. The rate of the reaction was measured as a function of substrate, FeBr3 and HNO3 concentration. From the experimental data a mechanism is suggested where there are two reaction pathways, one involving the formation of a ternary complex between the substrate, FeBr3 and NO 3- and one involving a complex formed between the sulfide and the HNO3. From these complexes HNO2 is generated, which then combines with HNO3 to yield N2O4, initiating a catalytic cycle where the sulfide is oxidized and O2 from the air is stoichiometrically consumed.
- Kinen, Claudio O.,Rossi, Laura I.,De Rossi, Rita H.
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experimental part
p. 7132 - 7139
(2009/12/09)
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- Catalytic sulfoxidation by dinuclear copper complexes
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The power of two: μ-η2:η2- Peroxodicopper(II) complexes with hexadentate diaminotetrabenzimidazole ligands can catalyze the sulfoxidation of aromatic sulfides by a direct oxygen-transfer mechanism (see scheme) in the presence of a sacrificial co-substrate, similarly to the enzyme tyrosinase. The yields and turnover numbers depend on the sulfide and co-substrate concentrations and the electron density on the sulfide S atom.
- Gamba, Ilaria,Palavicini, Sara,Monzani, Enrico,Casella, Luigi
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experimental part
p. 12932 - 12936
(2010/05/19)
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- Optimization of asymmetric oxidation of sulfides with the Fe(salan) complex in water and the expanded scope of its application
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The scope of asymmetric oxidation of sulfides using Fe(salan) complex as a catalyst and aqueous hydrogen peroxide as an oxidant in water was broadened by optimizing the reaction conditions with respect to reaction temperature, catalyst loading, and amount of water solvent. The oxidation proceeded with high enantioselectivity under the optimized conditions. The undesired over-oxidation of the resultant sulfoxides was significantly suppressed and the yields of sulfoxides were improved. Various functional groups were tolerant of the conditions.
- Egami, Hiromichi,Katsuki, Tsutomu
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experimental part
p. 1543 - 1546
(2009/04/07)
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- Ceric ammonium nitrate catalyzed oxidation of sulfides to sulfoxides
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Oxidation of sulfides to sulfoxides with a catalytic amount of ceric ammonium nitrate (CAN) reagent supported on silica gel has been achieved. Stoichiometric sodium bromate is utilized as the primary oxidant to continue the catalytic cycle involving CAN. Solid-supported CAN reagent allowed us to avoid using aqueous reaction media generally employed in CAN-promoted reactions. This heterogeneous CAN/NaBrO3 reagent has simplified the reaction work-up and product isolation, produced higher product yields, and shortened reaction times compared to reactions with homogeneous CAN reagents employing aqueous media. Georg Thieme Verlag Stuttgart.
- Ali, Mohammed Hashmat,Kriedelbaugh, Donna,Wencewicz, Timothy
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p. 3507 - 3511
(2008/09/19)
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- Self-catalyzed oxidation of sulfides with hydrogen peroxide: A green and practical process for the synthesis of sulfoxides
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A self-catalyzed selective oxidation of sulfides to sulfoxides has been developed. The scope of the protocol is demonstrated in the selective oxidation of 17 different substrates. High yields and chemoselectivity (in general > 90 % ) are achieved in most cases.
- Shi, Feng,Tse, Man Kin,Kaiser, Hanns Martin,Beller, Matthias
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p. 2425 - 2430
(2008/09/19)
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- Preparation and reactivity of polymer-supported 2-iodylphenol ethers, an efficient recyclable oxidizing system
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(Chemical Equation Presented) Preparation of new recyclable polymer-supported oxidizing reagents based on 2-iodylphenol ethers is described. The synthesis employs commercially available aminomethylated polystyrene or Merrifield resin and affords polymer-supported 2-iodylphenol ethers with loading up to 0.86 mmol/g with respect to IO2 groups. The new reagents effect clean and efficient conversion of a wide range of alcohols, including heteroatomic and unsaturated structures, to the corresponding carbonyl compounds. Recycling of the resins is possible with minimal loss of activity after several reoxidations.
- Karimov, Rashad R.,Kazhkenov, Zeinul-Gabiden M.,Modjewski, Matthew J.,Peterson, Eric M.,Zhdankin, Viktor V.
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p. 8149 - 8151
(2008/02/13)
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- Nitric acid in the presence of supported P2O5 on silica gel affords an efficient and mild system for oxidation of organic compounds under solvent-free conditions
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This paper describes an efficient and easy method for oxidation of alcohols 1 and sulfides 2 to their corresponding carbonyl compounds 3 and sulfoxides 4 with nitric acid in the presence of supported P2O5 on silica gel under solvent-free conditions in high yields.
- Hajipour, Abdol R.,Guo, Lian-Wang,Ruoho, Arnold E.
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- Selective oxidation of sulfides to sulfoxides and sulfones at room temperature using H2O2 and a Mo(VI) salt as catalyst
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Selective oxidation of sulfides to sulfoxides and sulfones is achieved by H2O2 using MoO2Cl2 as the catalyst. Various substituted sulfides having functional groups such as methyl, methoxy, bromo, nitro, alkene, alkyne, alcohol, ester, aldehyde and remarkably an oxime are successfully and selectively oxidized without affecting the sensitive functionalities.
- Jeyakumar, Kandasamy,Chand, Dillip Kumar
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p. 4573 - 4576
(2007/10/03)
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- 2-Iodylphenol ethers: Preparation, X-ray crystal structure, and reactivity of new hypervalent iodine(V) oxidizing reagents
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2-Iodylphenol ethers were prepared by the dimethyldioxirane oxidation of the corresponding 2-iodophenol ethers and isolated as chemically stable, microcrystalline products. Single-crystal X-ray diffraction analysis of 1-iodyl-2-isopropoxybenzene 8c and 1-iodyl-2-butoxybenzene 8d revealed pseudopolymeric arrangements in the solid state formed by intermolecular interactions between IO2 groups of different molecules. 2-Iodylphenol ethers can selectively oxidize sulfides to sulfoxides and alcohols to the respective aldehydes or ketones.
- Koposov, Alexey Y.,Karimov, Rashad R.,Geraskin, Ivan M.,Nemykin, Victor N.,Zhdankin, Viktor V.
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p. 8452 - 8458
(2007/10/03)
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- Facile preparation and reactivity of polymer-supported N-(2-lodyl-phenyl)- acylamide, an Efficient Oxidizing System
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(Chemical Equation Presented) A simple three-step preparation of polymer-supported N-(2-iodyl-phenyl)-acylamide (NIPA resin) starting from 2-iodoaniline is described. The resin was obtained with good loading levels (0.7-0.8 mmol g-1) and has been successfully used for efficient oxidation of a diverse collection of alcohols. Thus, treating alcohols with 1.0 equiv of the resin in 1,2-dichloroethane under reflux for 30-60 min allowed rapid and in most cases complete conversion to the corresponding carbonyl compound.
- Ladziata, Uladzimir,Willging, Jeff,Zhdankin, Viktor V.
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p. 167 - 170
(2007/10/03)
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- Nitric acid in the presence of supported P2O5 on silica gel: An efficient and novel reagent for oxidation of sulfides to the corresponding sulfoxides
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This paper describes an efficient and easy method for oxidation of sulfides 1 to their corresponding sulfoxides 2 with nitric acid in the presence of supported P2O5 on silica gel under solvent-free conditions in high yields.
- Hajipour, Abdol R.,Kooshki, Behzad,Ruoho, Arnold E.
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p. 5503 - 5506
(2007/10/03)
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- Polyvalent interactions in unnatural recognition processes
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The synthesis of two cluster compounds, one containing six secondary dialkylammonium ion centers and the other possessing six benzo-m-phenylene[25] crown-8 (BMP25C8) macrocycles, both appended to hexakis(thiophenyl)benzene cores, is described. The binding of these clusters with complementary mono- and divalent ligands is investigated with NMR spectroscopy to probe polyvalency in these unnatural recognition systems. The ability of the two different families of clusters to bind complementary monovalent ligands is compared with that of the monovalent receptor pair, namely the dibenzylammonium ion and BMP25C8. This comparison is made possible by determining an average association constant (KAVE) for the binding of each recognition site on the cluster with the corresponding monovalent ligand. We have found that the clustering of recognition sites together in one molecule is detrimental to their individual abilities to bind monovalent ligands. In the case of the polyvalent interaction between the hexakisBMP25C8 cluster and divalent dialkylammonium ions, an association constant, KPOLY, was calculated from the value of K AVE determined for the complexation of the individual component recognition sites. This polyvalent interaction is significantly stronger than that associated with the averaged monovalent interactions.
- Lowe, James N.,Fulton, David A.,Chiu, Sheng-Hsien,Elizarov, Arkadij M.,Cantrill, Stuart J.,Rowan, Stuart J.,Stoddart, J. Fraser
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p. 4390 - 4402
(2007/10/03)
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