- 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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- Nano copper catalyzed synthesis of symmetrical/unsymmetrical sulfones from aryl/alkyl halides and p-toluenesulfonylmethylisocyanide: TosMIC as a tosyl source
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A magnetically induced nano copper-catalyzed efficient and mild route for the synthesis of diaryl and alkyl/aryl sulfones from aryl/alkyl halides and tosylmethyl isocyanide (TosMIC) has been developed. A variety of aryl and alkyl sulfones have been obtained in very good to excellent yields. Sulfones containing molecules have medicinal relevance as they are known to possess various activities such as antifungal, anti-HIV, antitumor, and anticancer. Herein, a magnetically induced nano copper-catalyzed efficient and mild route for the synthesis of biaryl and alkyl/aryl sulfones from aryl/alkyl halides and tosylmethyl isocyanide (TosMIC) has been developed. A variety of aryl and alkyl sulfones have been obtained in very good to excellent yields. In this newly developed protocol TosMIC acts as sulfonyl source. The catalyst can magnetically be recovered and recycled five times without significant loss in activity.
- Phanindrudu, Mandalaparthi,Jaya, Pogula,Likhar, Pravin R.,Tiwari, Dharmendra Kumar
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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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- Selective Late-Stage Oxygenation of Sulfides with Ground-State Oxygen by Uranyl Photocatalysis
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Oxygenation is a fundamental transformation in synthesis. Herein, we describe the selective late-stage oxygenation of sulfur-containing complex molecules with ground-state oxygen under ambient conditions. The high oxidation potential of the active uranyl cation (UO22+) enabled the efficient synthesis of sulfones. The ligand-to-metal charge transfer process (LMCT) from O 2p to U 5f within the O=U=O group, which generates a UV center and an oxygen radical, is assumed to be affected by the solvent and additives, and can be tuned to promote selective sulfoxidation. This tunable strategy enabled the batch synthesis of 32 pharmaceuticals and analogues by late-stage oxygenation in an atom- and step-efficient manner.
- Li, Yiming,Rizvi, S. Aal-e-Ali,Hu, Deqing,Sun, Danwen,Gao, Anhui,Zhou, Yubo,Li, Jia,Jiang, Xuefeng
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supporting information
p. 13499 - 13506
(2019/08/21)
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- Sulfoxide and sulfone compounds, as well as selective synthesis method and application thereof
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The invention discloses a method for selectively synthesizing a sulfoxide compound shown as a formula (II) and a sulfone compound shown as a formula (III). In a reaction solvent, thioether (I) is usedas a reaction raw material and oxygen as an oxidation reagent, under the catalytic action of visible light and a photosensitive reagent; under the assistance of an additive, when a large-polarity proton-containing additive such as an acid and an alcohol or a solvent or an additive with excellent electron donating ability is used, a sulfoxide compound (II) is selectively generated; and when a small-polarity aprotic additive or a solvent is used, a sulfone compound (III) is selectively generated. The synthesis method has the advantages of easily available and cheap raw materials, simple reaction operation, mild reaction conditions, high yield and excellent functional group tolerance. According to the invention, synthesis and modification of some medicines are realized, and an efficient method for selectively constructing sulfoxide and sulfone compounds is provided for medicinal chemistry research.
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Paragraph 0049-0052
(2019/12/02)
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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 0042-0046
(2019/12/25)
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- Simple low cost porphyrinic photosensitizers for large scale chemoselective oxidation of sulfides to sulfoxides under green conditions: Targeted protonation of porphyrins
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Aerobic photooxidation of sulfides with the diacids of meso-tetra(phenyl)porphyrin, H2TPP (acid = CF3COOH, Cl2CHCOOH, HClO4 and H2SO4) under sunlight in acetonitrile gave the corresponding sulfoxides as nearly the exclusive product. The photocatalytic activity of the dications decreased as H4TPP(ClO4)2 ? H4TPP(Cl2CHCOO)2 ? H4TPP(CF3COO)2 > H4TPP(HSO4)2. Also, H4TPP(ClO4)2 and H4TPP(Cl2CHCOO)2 showed a remarkably increased oxidative stability in comparison with the free base porphyrin. The singlet oxygen quantum yield (φΔ) of the porphyrin diacids was found to be dependent on the acid used for the protonation of H2TPP. The solvent effect on the efficiency of the oxidation reaction was investigated using acetonitrile, 1,2-dichloroethane (DCE) and toluene. The higher conversions achieved in acetonitrile and DCE are in accord with the higher singlet oxygen lifetime in these solvents. Also, the lower fluorescence quantum yield of porphyrin dications in acetonitrile relative to that in DCE was used to explain the higher efficiency of the former. The porphyrin diacids can also accelerate the oxidation reaction through an acid catalysis mechanism. Also, cooxidation of methyl phenyl sulfide and diphenyl sulfide was conducted to provide insights into the nature of the active intermediates involved in the oxidation of sulfides to sulfoxides and partial overoxidation of the sulfoxides to sulfones. The results showed much higher reactivity of the persulfoxide intermediate compared to that of singlet oxygen. The catalytic system was successfully employed to the large scale preparation of sulfoxides from the corresponding sulfides under mild conditions.
- Mojarrad, Aida G.,Zakavi, Saeed
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p. 768 - 781
(2018/02/14)
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- Palladium(II)-Catalyzed Synthesis of Sulfinates from Boronic Acids and DABSO: A Redox-Neutral, Phosphine-Free Transformation
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A redox-neutral palladium(II)-catalyzed conversion of aryl, heteroaryl, and alkenyl boronic acids into sulfinate intermediates, and onwards to sulfones and sulfonamides, has been realized. A simple Pd(OAc)2 catalyst, in combination with the sulfur dioxide surrogate 1,4-diazabicyclo[2.2.2]octane bis(sulfur dioxide) (DABSO), is sufficient to achieve rapid and high-yielding conversion of the boronic acids into the corresponding sulfinates. Addition of C- or N-based electrophiles then allows conversion into sulfones and sulfonamides, respectively, in a one-pot, two-step process.
- Deeming, Alex S.,Russell, Claire J.,Willis, Michael C.
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supporting information
p. 747 - 750
(2016/02/27)
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- Application of a novel 1,3-diol with a benzyl backbone as chiral ligand for asymmetric oxidation of sulfides to sulfoxides
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A chiral 1,3-diol with a benzyl backbone has been used for the asymmetric oxidation of sulfides to sulfoxides. Moderate to good yields and enantioselectivity (upto 87% ee) have been observed.
- Gogoi, Paramartha,Kotipalli, Trimurthulu,Indukuri, Kiran,Bondalapati, Somasekhar,Saha, Pipas,Saikia, Anil K.
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supporting information; experimental part
p. 2726 - 2729
(2012/07/17)
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- 1-Butyl-3-methylimidazolium p-toluenesulfinate: A novel reagent for synthesis of sulfones and β-ketosulfones in ionic liquid
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A novel task-specific ionic liquid, 1-butyl-3-methylimidazolium p-toluenesulfinate, [bmim][p-TolSO2] has been synthesized and used as a nucleophile for the reaction with alkyl bromides and phenacyl bromides to prepare sulfones and β-ketosulfones in excellent yields (80-93%) in [bmim][BF4] ionic liquid. The isolated yields of sulfones and β-ketosulfones were higher in [bmim][BF4] than other organic solvents at room temperature.
- Kumar, Anil,Muthyala, Manoj Kumar
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p. 5368 - 5370
(2011/10/31)
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- Ti(iv)-amino triphenolate complexes as effective catalysts for sulfoxidation
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C 3-symmetric Ti (iv) amino triphenolate complexes efficiently catalyze, without previous activation and in excellent yields, the oxidation of sulfides at room temperature, using both CHP and the more environment friendly aqueous hydrogen peroxide as terminal oxidants, with catalyst loadings down to 0.01%. The Ti(iv) catalysts and the intermediate Ti(iv)-peroxo complexes have been characterized in solution by 1H NMR and ESI-MS techniques and via density functional studies.
- Mba, Miriam,Prins, Leonard J.,Zonta, Cristiano,Cametti, Massimo,Valkonen, Arto,Rissanen, Kari,Licini, Giulia
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experimental part
p. 7384 - 7392
(2010/09/17)
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- C3-symmetric Ti(IV) triphenolate amino complexes as sulfoxidation catalysts with aqueous hydrogen peroxide
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(Chemical Equation Presented) The Ti(IV) complex 2c bearing a C 3-symmetric triphenolate amine ligand is an air and moisture tolerant complex that efficiently catalyzes sulfoxidation reactions at room temperature without previous activation (catalyst loading down to 0.01%, TONs up to 8000, TOFs up to 1700 h-1, quantitative yields). Reactions were performed with aqueous hydrogen peroxide as oxidant, which adds value to the methodology from the environmental viewpoint.
- Mba, Myriam,Prins, Leonard J.,Licini, Giulia
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- Organic reactions in ionic liquids: An efficient method for the synthesis of aryl sulfones by alkylation of sodium arenesulfinates with alkyl halides
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An ionic liquid based on 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF4) is used as a reusable reaction medium for the alkylation of sodium arenesulfinates with alkyl halides. This procedure is convenient, efficient and generally gives rise to the S-alkylated product with high selectivity when applied to active halides.
- Hu, Yi,Chen, Zhen-Chu,Le, Zhang-Gao,Zheng, Qin-Guo
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p. 267 - 269
(2007/10/03)
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- Alanine/chlorochromic acid/silica gel: An efficient and selective reagent for the oxidation of organic functional groups
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Alanine / chlorochromic acid / silica gel is a new and selective reagent for the efficient oxidation of sulfides, thiols, oximes, and alcohols. Oxidation of sulfides is solvent dependent. In chloroform at room temperature sulfoxides are formed as the major products, while in carbon tetrachloride or under solvent-free conditions solfones are produced in good-to-excellent yields.
- Salehi, Peyman,Khodaei, Mohammad Mehdi,Rostami, Amin
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p. 2235 - 2243
(2007/10/03)
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- Organic reactions in ionic liquids: A new method for the synthesis of alkyl aryl sulfones by alkylation of sodium arenesulfinates with unactivated alkyl chlorides
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A new method is reported for the synthesis of alkyl aryl sulfones by alkylation of sodium arenesulfinates with unactivated alkyl chlorides using ionic liquid based on 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF 4) mixed with water (2:1) as reaction media. The ionic liquid can be reused and the procedure gives the sulfones in moderate yields.
- Hu, Yi,Chen, Zhen-Chu,Le, Zhang-Gao,Zheng, Qin-Guo
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p. 4031 - 4035
(2007/10/03)
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- Caro's acid supported on silica gel. IV. Facile synthesis of sulfones by the oxidation of various sulfides in aprotic solvent
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Oxidation of sulfides with Caro's acid supported on silica gel in acetonitrile gave sulfones in high to excellent yields under mild condition.
- Lakouraj, Moslem M.,Movassagh,Ghodrati
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p. 847 - 850
(2007/10/03)
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- Indium-catalysed aryl and alkyl sulfonylation of aromatics
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Commercially available indium (III) triflate is shown to be an extremely efficient catalyst for the sulfonylation of both activated and deactivated aromatics.
- Frost,Hartley,Whittle
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p. 830 - 832
(2007/10/03)
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- New procedures for the oxidation of sulfides to sulfoxides and sulfones
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New reagents for the oxidation of sulfides to the corresponding sulfoxides and sulfones are presented.
- Drabowicz, Jozef,Lyzwa, Piotr,Luczak, Jerzy,Mikolajczyk, Marian,Laur, Peter
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p. 425 - 426
(2007/10/03)
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- Polyethylene Glycol (PEG) 4000 Catalysed Regioselective Nucleophilic Ring Opening of Oxiranes - A New And Convenient Synthesis of β-Hydroxy Sulfone and β-Hydroxy Sulfide
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Oxiranes and sodium p-toluene sulfinate salt react smoothly in a regioselective manner in the presence of PEG4000 to furnish β-hydroxy sulfone and β-hydroxysulfide.The reaction was extended for the preparation of alkylsulfones and β-oxosulfones from alkylhalide and β-oxohalide respectively.
- Maiti, A. K.,Bhattacharyya, P.
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p. 10483 - 10490
(2007/10/02)
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- The remarkable effect of methanol on sulfide photooxidations. Evidence for its dual reactivity
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The addition of small amounts of methanol to photooxidation mixtures of sulfides dramatically enhances sulfone in preference to sulfoxide formation. High concentrations of methanol on the other hand have the opposite effect of promoting sulfoxide in prefe
- Clennan, Edward L.,Yang, Kang
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p. 1697 - 1700
(2007/10/02)
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- Sulfonylation of Organometallic Reagents with Arenesulfonyl Fluorides: A Simple One-Step Synthesis of Sulfones
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Sulfonylation of organometallic reagents was accomplished with arenesulfonyl fluorides to provide a wide variety of alkylaryl- and diaryl sulfones.Organolithium and diorganocopper lithium reagents react smoothly with arenesulfonyl fluorides to give sulfones in high yields.Alkyl Grignard reagents often lead to mixtures of monosulfonylated and disulfonylated products.However, allylmagnesium chloride and phenylmagnesium chloride provide the corresponding sulfones in excellent yields.Organocopper reagents were also found to yield sulfones upon treatment with arenesulfonyl fluorides.By utilizing this methodology, synthetically useful alkyl, (trimethylsilyl)methyl, and allyl sulfones are easily prepared in high yields.
- Frye, Leah L.,Sullivan, Eileen L.,Cusack, Kevin P.,Funaro, John M.
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p. 697 - 701
(2007/10/02)
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- Remote Participation during Photooxidation at Sulfur. Eidence for Sulfurane Intermediates
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The photooxidations of geminally substituted γ-hydroxy sulfides results in formation of unusual oxidative elimination products.Detailed spectral data and the independent synthesis of a close analogue provide compelling evidence for the structures of these
- Clennan, E. L.,Yang, Kang
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p. 4477 - 4487
(2007/10/02)
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- Efficient synthesis of sulphones using polysorbate-80 as phase transfer catalyst
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A very easy and practical method of preparing sulphones from alkyl halides has been developed using Polysorbate-80 as phase transfer catalyst.
- Biswas, Goutam K,Chakrabarty, Manas,Bhattacharyya, Prantosh
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- A simple and rapid preparation of sulfones from alkyl halides using ultrasound
-
Appropriate alkyl halides and sodium p-toluenesulfinates react rapidly in DMF-water at room temperature under the influence of ultrasound to afford sulfones. Using this procedure a wide variety of sulfones have been prepared.
- Biswas,Jash,Bhattacharyya
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p. 491 - 492
(2007/10/02)
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- A NEW GENERAL SYNTHESIS OF SULFONES FROM ALKYL OR ARYL HALIDES AND p-TOLUENESULFONHYDRAZIDE
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Here we report the utilization of commercially available p-toluenesulfonhydrazide as a new nucleophilic reagent in displacement reactions with suitable halides for an improved, general synthesis of sulfones.Good results are obtained with primary, secondary, allylic, benzylic, and aromatic halides activated by withdrawing groups.
- Ballini, Roberto,Marcantoni, Enrico,Petrini, Marino
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p. 6791 - 6798
(2007/10/02)
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- A Novel Synthesis of Alkyl Aryl Sulfones via the Telluride Ion-Assisted Coupling of Arenesulfonyl Chlorides with Alkyl Halides
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Arenesulfonyl chlorides undergo a facile one-pot coupling reaction with primary alkyl iodides and benzyl halides through the telluride ion-induced polarity reversal, giving the corresponding alkyl aryl sulfones in acceptable yields.
- Suzuki, Hitomi,Nishioka, Yoshinobu,Padmanabham, Seetharama Iyer,Ogawa, Takuji
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p. 727 - 728
(2007/10/02)
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- Microbial Oxidation of Alkyl Aryl Sulfides to the Corresponding Optically Active Sulfoxides
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Incubation of alkyl aryl sulfides with growing cells of Corynebacterium equi IFO 3730 afforded the corresponding sulfoxides and sulfones.The selectivity for the formation of sulfoxides over sulfones was higher with sulfides which have shorter alkyl chains.When methyl sulfides were used as substrates, formation of the corresponding sulfones was completely suppressed.Sulfoxides were revealed to have 87-100percent optically purities as to the (R) absolute configuration by HPLC analysis.The culture conditions seriously influenced the yield of oxidation products.High conversion of sulfides was attained when the reaction was carried out with grow ing cells in the logarithmic phase, in medium containing hexadecane as the carbon and energy source.
- Ohta, Hiromichi,Okamoto, Yasushi,Tsuchihashi, Gen-ichi
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p. 671 - 676
(2007/10/02)
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- SIMPLE AND CONVENIENT METHOD FOR THE SYNTHESIS OF SULFONES USING POLYETHYLENE GLYCOLS OR THEIR DIALKYL ETHERS AS SOLVENTS OR CATALYSTS.
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Various alkyl p-tolyl sulfones were prepared in good yields under mild conditions in the presence of polyethyene glycols or their dialkyl ethers as solvents or catalysts.
- Sukata
-
p. 613 - 614
(2007/10/02)
-
- ASYMMETRIC SYNTHESIS OF CHIRAL SULFOXIDES VIA MICROBIAL OXIDATION OF SULFIDES
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Incubation of alkyl aryl and allyl aryl sulfides with growing cells of Corynebacterium equi IFO 3730 gave the corresponding optically active sulfoxides with high enantiomeric excess.
- Ohta, Hiromichi,Okamoto, Yashushi,Tsuchihashi, Gen-ichi
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p. 205 - 208
(2007/10/02)
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- Substitution at Tetracoordinate Sulfur(VI). Rearrangement of 2-Aminoaryl Arenesulfonates to N-(2-Hydroxyaryl)arenesulfonamides
-
A series of eight 2-aminoaryl arenesulfonates upon treatment by strong bases rearranged intramolecularly to their corresponding N-(2-hydroxyaryl)arenesulfonamides as did the related tosylates derived from 2-amino-3-hydroxypyridine, 1-amino-2-naphthol, and
- Andersen, Kenneth K.,Gowda, Gopala,Jewell, Linda,McGraw, Phillip,Phillips, Brian T.
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p. 1884 - 1889
(2007/10/02)
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