- Cobalt-Catalyzed Redox-Neutral Sulfonylative Coupling from (Hetero)aryl Boronic Acids, Ammonium Salts and Potassium Metabisulfite
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An efficient cobalt-catalyzed redox-neutral sulfonylative coupling to afford (hetero)aryl alkyl sulfones from boronic acids, ammonium salts and potassium metabisulfite has been realized. Commercially available and air-stable CoCl2, in combination with phenanthroline ligand, is sufficient to achieve rapid and high-yielding conversion of the reactants into the corresponding sulfones. This practical transformation proceeds smoothly through C?N bond cleavage under redox-neutral catalytic conditions and shows broad functional-group tolerance. Other carbon based electrophiles, including diaryliodonium salts, heteroaryl halides, and carbonates were compatible. Further transformation of aryl alkyl sulfones then allows conversion into olefins, alkenyl sulfones and halogenated sulfones, respectively, in a one-pot process.
- Zhang, Yingying,Zhu, Haibo,Fan, Qiangwen,Yang, Liu,Xie, Zongbo,Le, Zhang-Gao
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- Synthesis of sulfone derivatives via palladium-catalyzed cross-coupling of benzyl trimethylammonium triflates and sulfonyl hydrazides
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A palladium-catalyzed cross-coupling of benzyl trimethylammonium triflates and sulfonyl hydrazides for the synthesis of various benzyl sulfones is reported. This novel protocol shows widespread functional group tolerance, leading to the desired sulfones in moderate to excellent yields.
- Luo, Jin,Wan, Juelin,Wang, Tao,Yu, Weijie
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supporting information
(2021/12/31)
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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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- Vanadium-catalyzed Selective Oxidation of Sulfides to Sulfoxides and Sulfones with H2O2
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Abstract: A direct selective approach to the oxidation of sulfides to sulfoxides andsulfones with H2O2 in moderate togood yields is developed. The reaction proceeds in the presence of 2 mol % ofVO(acac)2 at room temperature. All sulfoxides andsulfones were detected by gas chromatography, and the molecular structures of2-methylbenzyl 4-methylphenyl sulfone, 4-methylbenzyl 4-methylphenyl sulfone,2-bromobenzyl 4-methylphenyl sulfone, and 4-tert-butylbenzyl benzyl sulfone were determined by singlecrystal X-ray crystallography.
- Chen, M.,Jia, A.-Q.,Zhang, P.-Z.,Zhang, Q.-F.,Zhou, W.-Y.
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p. 816 - 824
(2021/06/12)
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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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- Silver-Catalyzed C(sp3)-H Sulfonylation for the Synthesis of Benzyl Sulfones Using Toluene Derivatives and α-Amino Acid Sulfonamides
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We describe a simple and practical protocol for the synthesis of benzyl sulfones using readily available toluene derivatives and α-amino acid sulfonamides. The reaction proceeds to afford a broad range of benzyl sulfones in moderate to high yields under silver catalysis. The mechanism possibly involves a Minisci-type formation of α-aminoalkyl radical, homolytic cleavage of a N-S bond to generate a sulfonyl radical, and coupling of sulfonyl radical with a benzyl radical formed via hydrogen abstraction by sulfate anion radical. The practicality of the present reaction is demonstrated by a gram-scale synthesis and one-step synthesis of anticancer-active compound. The mechanism studies are conducted using radical scavengers and deuterated toluene.
- Kanyiva, Kyalo Stephen,Shibata, Takanori,Uchida, Kanako
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p. 1377 - 1384
(2021/06/06)
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- One-pot synthesis of sulfones via Ni(II)-catalyzed sulfonylation of boronic acids, Na2S2O5 and benzylic ammonium salts
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A one-pot nickel-catalyzed synthesis of (hetero)aryl alkyl sulfones from readily available boronic acids, sodium metabisulfite and benzylic ammonium salts as electrophiles is described. This general and efficient synthetic process is of broad scope, occurs in two steps, and delivers structural diverse sulfones, and the intermediate sulfinate is isolated. The transformation exhibits application of benzylic ammonium salts as novel electrophiles for direct insertion of SO2 as a novel area to be investigated.
- Zhu, Haibo,Liu, Yishuai,Zhang, Yingying,Yang, Liu,Meng, Jia,Li, Qian,Gong, Bozhen,Xie, Zongbo,Le, Zhang-Gao
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- Photochemical Radical C–H Halogenation of Benzyl N-Methyliminodiacetyl (MIDA) Boronates: Synthesis of α-Functionalized Alkyl Boronates
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α-Haloboronates are useful organic synthons that can be converted to a diverse array of α-substituted alkyl borons. Methods to α-haloboronates are limiting and often suffer from harsh reaction conditions. Reported herein is a photochemical radical C-H halogenation of benzyl N-methyliminodiacetyl (MIDA) boronates. Fluorination, chlorination, and bromination reactions were effective by using this protocol. Upon reaction with different nucleophiles, the C?Br bond in the brominated product could be readily transformed to a series of C?C, C?O, C?N, C?S, C?P, and C?I bonds, some of which are difficult to forge with α-halo sp2-B boronate esters. An activation effect of B(MIDA) moiety was found.
- Yang, Ling,Tan, Dong-Hang,Fan, Wen-Xin,Liu, Xu-Ge,Wu, Jia-Qiang,Huang, Zhi-Shu,Li, Qingjiang,Wang, Honggen
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p. 3454 - 3458
(2020/12/17)
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- Visible-Light-Catalyzed in Situ Denitrogenative Sulfonylation of Sulfonylhydrazones
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A photocatalyzed in situ denitrogenative sulfonylation of N-arylsulfonyl hydrazones has been developed. This transformation provides a low-carbon strategy to assemble arylalkyl sulfones in a stepwise denitrogenation/sulfonylation manner.
- Huang, Xiang,Chen, Xing,Xie, Haisheng,Tan, Zheng,Jiang, Huanfeng,Zeng, Wei
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supporting information
p. 6784 - 6788
(2021/09/08)
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- Curbed of molybdenum oxido-diperoxido complex on ionic liquid body of mesoporous Bipy-PMO-IL as a promising catalyst for selective sulfide oxidation
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In this work, we introduce a novel bipyridinium ionic liquid bridged periodic mesoporous organosilicas (Bipy-PMOs-IL) which is used as the support to immobilize oxygen-rich Molybdenum (VI)-based oxido-peroxido complex (MoO(O2)2?Bipy-PMO-IL). Several techniques such as Small-angle X-ray scattering (SAXS), low angle XRD, FE-SEM (field emission scanning electron microscope), TEM (transmission electron microscope), N2 adsorption-desorption analyses (BET), atomic absorption spectroscopy (AAS), Fourier-transform infrared spectroscopy (FT-IR) and Energy Dispersive X-Ray (EDS or EDX) were used to characterize this nanomaterial. Also, the catalytic activities of the MoO(O2)2?Bipy-PMO-IL as a hybrid catalyst is tested in the selective oxidation of sulfides in water by using H2O2 (30%) as an eco-friendly and green co-oxidant. The as-prepared novel catalyst shows high to excellent performance under optimum reaction conditions at ambient room temperature. The obtained results in this work show several outstanding advantages, such as green conditions, high product yields, easy work-up, easy preparation and acceptable reusability of the catalyst for at least 5 runs. To study the IL effect in immobilization of Mo-complex, in a comparison study, the MoO(O2)2?Bipy-PMO-IL materials and MoO(O2)2?SBA-15 (with simple SiO2 body, no IL) body were employed for sulfide oxidation. After the treatment, the Mo?Bipy-PMO-IL with IL body in channels was reused for subsequent experiments (5 runs), but in Mo?SBA-15 after second run the yield was decreased dramatically.
- Ahadi, Arefeh,Dugheri, Stefano,Hasanzadeh, Amir,Kavetskyy, Taras,Khaksar, Samad,Mamba, Bhekie B.,Moaser, Azra Ghiasi,Msagati, Titus A.-M.,Rostamnia, Sadegh,Rouhani, Shamila,Shokouhimehr, Mohammadreza
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- Novel Method for Preparing Xanthone Derivatives, Novel Xanthone Derivatives Made thereby, and Composition Comprising the Same
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The present invention relates to a method for manufacturing a novel xanthone derivative, the xanthone derivative manufactured therefrom, and use thereof. The method according to the present invention is a single step process without using a transition met
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Paragraph 0152; 0180-0185
(2020/03/03)
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- Ag?CeO2 nanoparticles with “rice ball” configuration as an efficient and heterogeneous nanocatalyst for the selective oxidation of sulfides to sulfones with 30% H2O2
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Abstract: Ag?CeO2 with a rice-ball configuration as a heterogeneous and highly efficient catalyst was described for activation of H2O2 in the selective oxidation of aromatic and aliphatic sulfides to their corresponding sulfones. Ag nanoparticles in the CeO2–Ag interface increase the oxygen vacancy defects on the surface of CeO2 and oxygen vacancy defects promote the reduction of Ce4+ to Ce3+ to keep the electroneutrality. Generated Ce3+ species act as the active sites in the interface of CeO2–Ag to promote the oxidation of sulfides to sulfones. Compatibility with various aromatic and aliphatic sulfides, excellent selectivity, high yield of product, simple experimental procedure, and mild reaction conditions are some of the precious advantages of Ag?CeO2/H2O2 catalyst system. Graphic abstract: [Figure not available: see fulltext.]
- Bahrami, Kiumars,Ghorbani, Somayeh,Parnian, Rouhallah,Soleimani, Ebrahim
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- Base-controlled divergent synthesis of vinyl sulfones from (benzylsulfonyl)benzenes and paraformaldehyde
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A tuneable metal-free protocol for the selective preparation of a-substituted vinyl sulfone and (E)-vinyl sulfone derivatives has been described. In this process, stable paraformaldehyde was used as the carbon source. The base played an important role in the selectivity control of transformations. More than 50 products were synthesized with excellent chemoselectivity and broad functional group tolerance.
- Xiao, Fuhong,Hu, Yangling,Huang, Huawen,Xu, Fen,Deng, Guo-Jun
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supporting information
p. 3527 - 3535
(2020/05/25)
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- Method for synthesizing organic sulfone molecules by using novel sulfone benzylation 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 benzylation reagent. Easilyavailable sulfonylhydrazine and dibenzyl phosphite are taken as initial reaction raw materials, N,N-dimethylformamide (DMF) is taken as a reaction medium, sodium iodide (NaI) is taken as a catalyst, and organic sulfone molecules are synthesized through reaction at 60 DEG C, wherein dibenzyl phosphite is a novel sulfone benzylation reagent. The method has the advantages that the raw materials are cheap and easy to obtain, the method can be amplified to gram-level reaction to synthesize the active organic sulfone molecule with the sulfone benzyl structure, complex reaction conditions such as anytransition metal catalyst are not needed in the reaction, and heavy metal residues of the synthesized active drug molecule and pollution to the environment are avoided.
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Paragraph 0008; 0010; 0016-0018
(2020/12/31)
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- Cu2O-catalyzed C–S coupling of quaternary ammonium salts and sodium alkane-/arene-sulfinates
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A new protocol for the synthesis of (enantioenriched) benzylic sulfones via the Cu2O-catalyzed C–S bond cross coupling of alkane-/arene-sulfinates and (enantioenriched) benzylic quaternary ammonium salts has been developed. The product benzylic sulfones were obtained in good to high yields (75–96%). Chiral arylmethyl sulfones with high enantiomeric excess (90–94% ee) were also synthesized in the presence of Cu2O and 1,1′-bis-(diphenylphosphino)ferrocene (dppf).
- Chen, Hongyi,Huang, Youming,Zeng, Qingle,Zheng, Wenting
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- Multicomponent Synthesis of Sulfones and Sulfides from Triarylbismuthines and Sodium Metabisulfite in Deep Eutectic Solvents
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This study describes a novel and catalyst-free methodology for the multicomponent synthesis of a broad range of sulfones, disulfides, and sulfides from non-toxic triarylbismuthines (Ar3Bi) and sodium metabisulfite (Na2S2O5) in deep eutectic solvents (DESs). The fine tuning of the DESs properties allowed the solubility of all reagents, enhancing their reactivity, as well as, the recyclability of the reaction medium for at least 5 consecutive cycles. Thus, this versatile strategy uses non-toxic reagents without the need of metal catalysts in a sustainable solvent, being an interesting alternative to traditional hazardous protocols.
- Saavedra, Beatriz,Marset, Xavier,Guillena, Gabriela,Ramón, Diego J.
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supporting information
p. 3462 - 3467
(2020/06/04)
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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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- A general and practical sulfonylation of benzylic ammonium salts with sulfonyl hydrazides for the synthesis of sulfones
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A practical and efficient approach adopting transition-metal-free cross-coupling of sulfonyl hydrazides with benzyl ammonium salts has been developed to synthesize benzyl sulfones using Cs2CO3 as base under mild conditions. The protocol employs stable and easy to handle coupling partners, and is endowed with good substrate compatibility, leading to functional benzyl sulfones in good yields.
- Zhu, Haibo,Zhang, Yingying,Liu, Yishuai,Yang, Liu,Xie, Zongbo,Jiang, Guofang,Le, Zhang-Gao
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- Rhodium Porphyrin Catalyzed Regioselective Transfer Hydrogenolysis of C-C σ-Bonds in Cyclopropanes with iPrOH
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A new rhodium porphyrin catalyzed regioselective transfer hydrogenolysis of both activated and unactivated cyclopropanes employing iPrOH as the hydrogen source was discovered. The reaction mechanism for the C-C σ-bond activation of cyclopropanes was identified through an initial radical substitution with rhodium(II) metalloporphyrin radical to give a rhodium porphyrin alkyl, followed by hydrogenolysis with iPrOH to give the corresponding acyclic alkanes and regenerate rhodium(II) metalloporphyrin radical.
- Chen, Chen,Feng, Shiyu,Chan, Kin Shing
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supporting information
p. 2582 - 2589
(2019/07/02)
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- Umpolung cross-coupling of polyfluoroarenes with hydrazones: Via activation of C-F bonds
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An umpolung strategy for the cross-coupling of polyfluoroarenes with various substituted hydrazones to construct C(sp2)-C(sp3) bonds is developed. In this strategy, the C-F bond of polyfluoroarenes is cleaved and coupled with moisture- and air-stable hydrazones under mild conditions with good to excellent yields. This method provides a useful tool for synthesizing polyfluorinated pharmaceuticals and functional materials.
- Cao, Dawei,Pan, Pan,Zeng, Huiying,Li, Chao-Jun
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supporting information
p. 9323 - 9326
(2019/08/08)
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- A multifunctional Co-based metal-organic framework: heterogeneous catalysis, chemiluminescence sensing and moisture-dependent solvatochromism
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Crystalline materials with multi-catalytic applications are of great value to both fundamental research and practical applications. The platform of metal-organic frameworks (MOFs) is utilized to fabricate a microporous versatile catalyst with high stability. Self-assembly of a flexible ligand, 4-(4-carboxybenzylamino)benzoic acid (H2CBBA), with Co(ii) resulted in a 3D framework, CBBA-Co, with Co3O clusters exposed in the zigzag channels. Upon in situ activation, CBBA-Co exhibited multiple heterogeneous catalytic activities. Theoretical calculations were carried out to give insights into the catalytic process. In addition, CBBA-Co also showed promising potential in optical sensing by virtue of its catalytic activity. The luminol chemiluminescence was greatly enhanced by CBBA-Co, and linear determination of the concentration of H2O2 in the range of 0-30% was established. The successful implementation of CBBA-Co indicates the feasibility and promising future of employing MOFs as an efficient platform for the fabrication and study of multifunctional catalysts, both experimentally and theoretically.
- Xie, Ming-Hua,Wang, Ya,Li, Ruo-Fei,Dong, Peng-Yu,Hou, Gui-Hua,Shao, Rong,Xi, Xin-Guo,Guan, Rong-Feng,Yang, Xiu-Li
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p. 12406 - 12413
(2018/09/25)
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- Reusable BNPs-SiO2@(CH2)3NHSO3H-catalysed selective oxidation of sulfides to sulfones
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Reusable boehmite nanoparticles–silica–NHSO3H (BNPs-SiO2@(CH2)3NHSO3H) was found to be an efficient heterogeneous nanocatalyst for the selective oxidation of sulfides to sulfones in the presence of H2O2. Excellent yields, easy and quick isolation of products, short reaction times and excellent selectivity are the main advantages of this method. The catalyst was characterized using Fourier transform infrared spectroscopy, energy-dispersive X-ray analysis, X-ray diffraction, and transmission and scanning electron microscopies.
- Bahrami, Kiumars,Khodamorady, Minoo
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- Synthetic method for preparing thiosulfonates on basis of sulfinic acid sodium salt disproportionated reaction
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The invention relates to a synthetic method for preparing thiosulfonates on the basis of a sulfinic acid sodium salt disproportionated reaction. The preparation method comprises the steps that sulfinic acid sodium salts serve as the raw materials, boron trifluoride diethyl etherate serves as accelerant, dichloromethane serves as solvent, and by means of a disproportionation coupled reaction, a thiosulfinate compound with good biological activity is synthesized; two different sulfinic acid sodium salts serve as the raw materials, and by means of a crossed disproportionation coupled reaction method, an asymmetric thiosulfinate compound can be synthesized. By means of a one-pot method and a two-step method, and by means of a thiosulfonates intermediate prepared on site, a sulfones compound and a sulfonamides compound can be synthesized by directly starting from sulfinic acid sodium salts. Accordingly, a synthetic route for preparing thiosulfonates on the basis of the sulfinic acid sodiumsalt disproportionated reaction is provided for the first time, operation is easy, raw materials are easy to obtain, the condition is mild, no metal catalyst is needed, no additional oxidant or reductant is needed, and the prepared thiosulfonates can have the good biological activity, and can also serve as the intermediate of the reaction to be applied to organic synthesis.
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Paragraph 0065; 0066; 0068
(2018/10/19)
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- Disproportionate Coupling Reaction of Sodium Sulfinates Mediated by BF3·OEt2: An Approach to Symmetrical/Unsymmetrical Thiosulfonates
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The BF3·OEt2-mediated disproportionate coupling reaction of sodium sulfinates was found for the first time. In this reaction, various S-S(O)2 bonds can be formed, efficiently giving thiosulfonates in moderate to excellent yields. As a convenient protocol for the synthesis of symmetrical and unsymmetrical thiosulfonates, its reaction mechanism involves the formation of a thiyl radical and sulfonyl radical via a sulfinyl radical disproportionation. What is more, this transformation can also be applied practically as a gram-scale reaction and to the two-step synthesis of sulfone and sulfonamide in one pot in situ using thiosulfonate as an intermediate.
- Cao, Liang,Luo, Shi-He,Jiang, Kai,Hao, Zhi-Feng,Wang, Bo-Wen,Pang, Chu-Ming,Wang, Zhao-Yang
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p. 4754 - 4758
(2018/08/24)
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- MANUFACTURING METHOD OF COMPOUND HAVING SULFONYL GROUP
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The present invention relates to a method for manufacturing a compound having a sulfonyl group, which includes a step for reacting thiosulfonates in a solvent comprising nucleophilic bases with an electrophilic agent. Accordingly, the present invention can manufacture the compound having the sulfonyl group with a variety of structures with high efficiency and high yield through more simplified processes than conventional methods.COPYRIGHT KIPO 2018
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Paragraph 0108; 0109; 0165-0168
(2018/10/03)
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- Synthesis of Sulfones and Sulfonamides via Sulfinate Anions: Revisiting the Utility of Thiosulfonates
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Simple and high-yielding strategies for the production of a variety of sulfones and sulfonamides, using thiosulfonates synthesized by copper-catalyzed aerobic dimerization, are reported. Although thiosulfonates are an old class of compound, practical methods for their synthesis and utilization have not been rigorously developed. In this study, we revisit the reactions of easily accessible thiosulfonates to form sulfinate anions. Because of the similar reactivity of thiosulfonates and metal sulfinates derived from toxic SO2, thiosulfinates are proposed to be stable, nontoxic alternatives to metal sulfinate salts.
- Shyam, Pranab K.,Jang, Hye-Young
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p. 1761 - 1767
(2017/02/10)
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- 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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- Efficient synthesis of aliphatic sulfones by Mg mediated coupling reactions of sulfonyl chlorides and aliphatic halides
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Sulfonyl chlorides were reduced to anhydrous sulfinate salts with magnesium under sonication. These sulfinates were alkylated to sulfones with alkyl chlorides in the presence of catalytic sodium iodide under sonication. A variety of aliphatic sulfones was efficiently prepared by this one-pot two-step procedure.
- Fu, Ying,Xu, Qin-Shan,Li, Quan-Zhou,Du, Zhengyin,Wang, Ke-Hu,Huang, Danfeng,Hu, Yulai
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supporting information
p. 2841 - 2845
(2017/04/03)
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- Application of sodium titanate nanotubes doped with vanadium (VNaTNT) as a heterogeneous catalyst for oxidation of sulfides at room temperature
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A heterogeneous titanate nanotube (TNT) catalyst containing TiO2, Na, and V has been synthesized and used in the chemoselective oxidation of sulfides to the corresponding sulfoxides in the presence of 30% H2O2 in water. Some of the advantages of our method include excellent yields, heterogeneous conditions, simplicity, compatibility with a variety of functionalities, and ease of isolation of the products. Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and N2 adsorption were used for structural and textural characterization of the catalyst (VNaTNT).
- Dadvar, Mohammad Ali,Fazaeli, Razieh
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p. 494 - 501
(2016/04/20)
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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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- Iron(III) phthalocyanine-chloride-catalyzed synthesis of sulfones from sulfonylhydrazones
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In this study, sulfones are synthesized from sulfonylhydrazones catalyzed by iron(III) phthalocyanine chloride. This reaction offers broad substrate scope, occurs under mild conditions, utilized readily available reactants, and forms products in good-to-h
- Zhao, Jun-Long,Guo, Shi-Huan,Qiu, Jun,Gou, Xiao-Feng,Hua, Cheng-Wen,Chen, Bang
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supporting information
p. 2375 - 2378
(2016/05/19)
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- Palladium-Catalyzed Synthesis of (Hetero)Aryl Alkyl Sulfones from (Hetero)Aryl Boronic Acids, Unactivated Alkyl Halides, and Potassium Metabisulfite
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A palladium-catalyzed one-step synthesis of (hetero)aryl alkyl sulfones from (hetero)arylboronic acids, potassium metabisulfite, and unactivated or activated alkylhalides is described. This transformation is of broad scope, occurs under mild conditions, and employs readily available reactants. A stoichiometric experiment has led to the isolation of a catalytically active dimeric palladium sulfinate complex, which was characterized by X-ray diffraction analysis.
- Shavnya, Andre,Hesp, Kevin D.,Mascitti, Vincent,Smith, Aaron C.
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supporting information
p. 13571 - 13575
(2015/11/16)
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- Nickel(II), copper(II), and cobalt(II) complexes derived from a new unsymmetrical ONS donor schiff base ligand: Synthesis, characterization, crystal structure, and catalytic activities
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A series of Ni(II), Cu(II), and Co(II) complexes, ML2, of a new thioether containing ONS donors have been synthesized, where L = deprotonated Schiff base. The analytical, spectral (FTIR,1H NMR, UV–vis), conductivity, and magnetic stu
- Kalita, Mukul,Gogoi, Prasanta,Barman, Pranjit,Sarma, Bipul
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p. 2445 - 2454
(2014/10/15)
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- Application of the polyacrylonitrile fiber as a support for the green heterogeneous base catalyst and supported phase-transfer catalyst
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A facile synthesized polyethylene polyamine functionalized polyacrylonitrile fiber (PANF-PA), capable of acting as the heterogeneous base catalyst and supported phase-transfer catalyst (SPTC), was presented in Knoevenagel condensation-cyclization and nucleophilic substitution for the synthesis of a number of substituted iminocoumarins and sulfones in aqueous systems, respectively. Excellent results are shown in terms of simple procedures, high chemical yields (up to 96%), extensive applicability and superior catalytic recyclability even for 10 cycles. The deeper active principle of the PANF-PA as SPTC was explained through detailed characterization by means of elemental analysis, FTIR spectroscopy and SEM. Moreover, the procedures can be effectively scaled up, and the solvent can be easily recovered. As well as, the prominent features (high strength, good flexibility etc.) of the polyacrylonitrile fiber are very attractive for fixed-bed reactors in the chemical industry. This journal is
- Shi, Xian-Lei,Tao, Minli,Lin, Huikun,Zhang, Wenqin
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p. 64347 - 64353
(2015/02/19)
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- Application of fundamental organometallic chemistry to the development of a gold-catalyzed synthesis of sulfinate derivatives
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The development of a gold(I)-catalyzed sulfination of aryl boronic acids is described. This transformation proceeds through an unprecedented mechanism which exploits the reactivity of gold(I)-heteroatom bonds to form sulfinate anions. Further in situ elaboration of the sulfinate intermediates leads to the corresponding sulfones and sulfonamides, two pharmacophores routinely encountered in drug discovery. A la mode: A gold(I)-catalyzed synthesis of sulfinates has been accomplished. Preparation of proposed intermediates, X-ray studies, and a number of mechanistic experiments suggest that an unprecedented mode of reactivity for gold(I) has been achieved. The resulting sulfinates from this reaction can be functionalized in situ to form sulfones and sulfonamides.
- Johnson, Miles W.,Bagley, Scott W.,Mankad, Neal P.,Bergman, Robert G.,Mascitti, Vincent,Toste, F. Dean
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supporting information
p. 4404 - 4407
(2014/05/06)
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- Palladium-catalyzed intramolecular oxidative coupling involving double C(sp2)-H bonds for the synthesis of annulated biaryl sultams
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The palladium-catalyzed intramolecular oxidative coupling described herein involves a double C(sp2)-H bond functionalization in sulfonanilides, providing a workable access to biaryl sultams annulated into a six-membered ring that are otherwise difficult to obtain by literature methods. The other synthetic applications of this protocol including the synthesis of biaryl sultams containing a seven-membered ring and analogous sultones are also presented.
- Laha, Joydev K.,Jethava, Krupal P.,Dayal, Neetu
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p. 8010 - 8019
(2015/03/18)
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- One-pot synthesis of multifunctionalized cyclopropanes
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A facile one-step synthetic protocol toward multifunctionalized cyclopropanes 4 is developed from substituted chalcones 1 and sulfones 2 in good yields via a [2C+1C] annulation.
- Chang, Meng-Yang,Chen, Yi-Chia,Chan, Chieh-Kai
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p. 2257 - 2263
(2014/03/21)
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- Synthesis of arylethyl (E)-styrylsulfones and arylsulfones by one-pot DIBAL-H/NaH-mediated reaction of β-ketosulfones
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A facile one-pot synthetic route for preparing a series of arylethyl (E)-styrylsulfones or arylethyl arylsulfones is developed. The efficient one-pot DIBAL-H/NaH-mediated route includes reduction of α-benzyl-β- arylketosulfones and retroaldol/aldol or retro aldol reaction of the resulting intermediate. The DIBAL-H/NaH-mediated reaction mechanism has been discussed. Georg Thieme Verlag Stuttgart. New York.
- Chang, Meng-Yang,Chen, Yi-Chia,Chan, Chieh-Kai
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p. 1739 - 1744
(2014/08/05)
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- CuI catalyzed sulfonylation of organozinc reagents with sulfonyl halides
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In this study, a facile CuI catalyzed synthesis of sulfones involving a nucleophilic addition of functionalized organozinc reagents to organic sulfonyl chlorides is realized. This reaction proceeds efficiently at room temperature, giving rise to various functional group substituted sulfones, generally in moderate to high yields. The method provides a novel, simple, and promising strategy for functionalized sulfone synthesis in the research field of sulfur chemistry. the Partner Organisations 2014.
- Fu, Ying,Zhu, Wenbo,Zhao, Xingling,Huegel, Helmut,Wu, Zhouqiang,Su, Yuhu,Du, Zhengyin,Huang, Danfeng,Hu, Yulai
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p. 4295 - 4299
(2014/06/23)
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- Palladium-catalyzed desulfitative cross-coupling reaction of sodium sulfinates with benzyl chlorides
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A palladium-catalyzed approach for the synthesis of diarylmethanes from sodium sulfinates and benzyl chlorides is described. Various aromatic sodium sulfinates were used as aryl sources via extrusion of SO2 and gave the diarylmethanes in moderate to good yields.
- Zhao, Feng,Tan, Qi,Xiao, Fuhong,Zhang, Shufeng,Deng, Guo-Jun
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p. 1520 - 1523
(2013/06/26)
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- One-pot three-component sulfone synthesis exploiting palladium-catalysed aryl halide aminosulfonylation
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A palladium-catalysed aminosulfonylation process is used as the key-step in a one-pot, three-component sulfone synthesis. The process combines aryl-, heteroaryl- and alkenyl iodides with a sulfonyl unit and an electrophilic coupling fragment. The sulfonyl unit is delivered in the form of an aminosulfonamide, which then serves as a masked sulfinate. The sulfinate is combined, in situ, with an electrophilic coupling partner, such as a benzylic, allylic or alkyl halide, an electron-poor arene, or a cyclic epoxide, to provide the corresponding sulfone products in good to excellent yields. The mild reaction conditions and use of commercially available reaction components allows the easy preparation of a broad range of sulfones featuring a variety of functional groups. The process obviates the need to employ thiol starting materials, and oxidative operations.
- Richards-Taylor, Charlotte S.,Blakemore, David C.,Willis, Michael C.
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p. 222 - 228
(2014/01/06)
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- Nano-rod catalysts: Building MOF bottles (MIL-101 family as heterogeneous single-site catalysts) around vanadium oxide ships
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Porous materials based on chromium (III) terephthalate metal organic frameworks (Cr-MIL(101)) and their new composites with vanadium oxide has emerged as a potential catalyst because of its high specific surface area, tunable pore size, and unique structure. The structural and textural characterization of V@MIL(101) were done using FTIR, X-ray diffraction, N 2 adsorption-desorption, and TEM. XRD and adsorption-desorption analysis shows that the mesostructure of MIL-101 remains intact after vanadium oxide modifications, while spectral technique show the successful immobilizing of the neat vanadium oxide inside the MIL-101 cavities. These new catalysts were found to be highly effective for selective oxidation of sulfides to sulfoxides and sulfones with H2O2 at room temperature and the 4.2% V@MIL(101) catalyst showed the highest activity. The PW12@MCF im heterogeneous system showed high catalytic oxidative activity in the treatment of commodity gasoline.
- Fazaeli, Razieh,Aliyan, Hamid,Moghadam, Majid,Masoudinia, Mona
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- Polyvinylpolypyrrolidone-supported boron trifluoride (PVPP-BF3): Highly efficient catalyst for chemoselective oxygenation of sulfides to sulfones by H2O2
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A highly efficient method for the oxidation of sulfides to sulfones using polyvinylpolypyrrolidone-supported boron trifluoride (PVPP-BF3) in the presence of (35%) hydrogen peroxide has been developed. This procedure cleanly oxidizes dialkyl and alkyl aryl sulfides to the corresponding sulfones in excellent yields at room temperature.
- Mokhtary, Masoud,Lakouraj, Moslem Mansour,Niaki, Masoumeh Rastegar
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experimental part
p. 321 - 326
(2012/03/27)
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- Host (aluminum incorporated mesocellulous silica foam (Al-MCF))-guest (tungsten polyoxometalate) nanocomposite material: An efficient and reusable catalyst for selective oxidation of sulfides to sulfoxides and sulfones
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A green, efficient and selective approach for the oxidation of sulfides to sulfoxides and sulfones with H2O2 at room temperature is reported. The reaction is performed in the presence of tungstophosphoric acid (PW12) supported on an aluminum incorporated mesocellulous silica foam (Al-MCF) (via both: the impregnation and encapsulation methods), as heterogeneous and reusable catalysts. The structural and textural characterizations of these catalysts were done using FTIR, X-ray diffraction, N2 adsorption-desorption and TEM.
- Fazaeli, Razieh,Aliyan, Hamid,Ahmadi, Mohammad Ali,Hashemian, Saeedeh
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- Insights into sulfinate formation from tosyl hydrazides
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Benzylation of 1,2-ditosylhydrazine in DMF under various basic conditions results in a benzyl sulfone via intermediary sulfinate formation, providing new insights and allowing practical conclusions to be drawn. The half-lives of 1,2-ditosylhydrazine and several monotosylated hydrazides with 1,1,3,3-tetramethylguanidine in DMSO have been determined by 1H NMR spectroscopy and are found to vary from a few minutes to several months. In the course of this work a benzylated, partly detosylated compound has been identified and a 1,1,3,3-tetramethyl guanidine-containing side-product characterized. A contradictory report is also commented on.
- Ragnarsson, Ulf,Grehn, Leif
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p. 1045 - 1047
(2012/03/27)
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- Zinc-mediated tandem-one-pot facile synthesis of 1-(arylsulfonyl) aryl/heteryl methanes: A case of C-S bond formation
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Reaction of arylmethyl/heteryl methyl zinc chloride (generated in situ from aryl methyl and heteryl methyl chloride and zinc metal) with aryl sulfonyl chlorides in tetrahydrofuran (THF) under mild conditions (i.e., at room temperature) furnishes the corresponding 1-(aryl sulfonyl)aryl/heteryl methanes in good yields.
- Srinivas,Dubey
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experimental part
p. 1584 - 1592
(2011/06/27)
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- Preliminary investigations on novel camphor-derived chiral sulfones: Completely stereoselective formation of tricyclic β-hydroxy sulfones from 8- and 10-functionalized camphor derivatives
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Some camphor-derived chiral allylic and benzylic sulfones in which the sulfonyl group is located at the C-10, C-9 or C-8 methyl groups of (+)-camphor were synthesized. The C-9 and C-8 substituted sulfones were obtained via Wagner-Meerwein rearrangements of the bicyclic camphor framework. On treatment with LDA, the C-10 and C-8 substituted sulfones cyclized with complete stereoselectivity, affording tricyclic β-hydroxy sulfones whose relative configurations were determined by X-ray crystallography. Tricyclic sulfones 23 and 24 underwent both β-elimination and retro-aldol reactions on further exposure to base. Reduction of the carbonyl group of the C-10 substituted sulfones afforded exo-configured isobornyl sulfones with high stereoselectivity. Reaction of the lithiated isobornyl benzyl sulfone 32 with benzaldehyde generated all four of the possible product diastereomers, of which three were isolated pure by chromatography. Attempted desulfonylation of these diastereomers failed to generate the desired optically active homobenzylic alcohols but the same sulfonyl carbanion trapping/desulfonylation sequence was successful in a model achiral series of compounds.
- Lewis, Frank W.,McCabe, Thomas C.,Grayson, David H.
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supporting information; experimental part
p. 7517 - 7528
(2011/10/12)
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