- Preparation of Recyclable and Versatile Porous Poly(aryl thioether)s by Reversible Pd-Catalyzed C–S/C–S Metathesis
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Porous organic materials (polymers and COFs) have shown a number of promising properties; however, the lability of their linkages often limits their robustness and can hamper downstream industrial application. Inspired by the outstanding chemical, mechanical, and thermal resistance of the 1D polymer poly(phenylene sulfide) (PPS), we have designed a new family of porous poly(aryl thioether)s, synthesized via a mild Pd-catalyzed C–S/C–S metathesis-based method, that merges the attractive features common to porous polymers and PPS in a single material. In addition, the method is highly modular, allowing to easily introduce application-oriented functionalities in the materials for a series of environmentally relevant applications including metal capture, metal sensing, and heterogeneous catalysis. Moreover, despite their extreme chemical resistance, the polymers can be easily recycled to recover the original monomers, offering an attractive perspective for their sustainable use. In a broader context, these results clearly demonstrate the untapped potential of emerging single-bond metathesis reactions in the preparation of new, recyclable materials.
- Morandi, Bill,Rivero-Crespo, Miguel A.,Toupalas, Georgios
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supporting information
p. 21331 - 21339
(2021/12/17)
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- Heterogeneously Ni-Pd nanoparticle-catalyzed base-free formal C-S bond metathesis of thiols
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This study rationally designed a heterogeneously catalyzed system (i.e., using Ni-Pd alloy nanoparticles supported on hydroxyapatite (Ni-Pd/HAP) under an H2atmosphere) achieving an efficient base-free formal C-S bond metathesis of various thiolsviasuppression of the Ni catalysis deactivation.
- Mitamura, Kanju,Yatabe, Takafumi,Yamamoto, Kidai,Yabe, Tomohiro,Suzuki, Kosuke,Yamaguchi, Kazuya
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supporting information
p. 3749 - 3752
(2021/04/21)
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- Dechalcogenization of Aryl Dichalcogenides to Synthesize Aryl Chalcogenides via Copper Catalysis
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An application for dechalcogenization of aryl dichalcogenides via copper catalysis to synthesize aryl chalcogenides is disclosed. This approach is highlighted by the practical conditions, broad substrate scope, and good functional group tolerance with several sensitive groups such as aldehyde, ketone, ester, amide, cyanide, alkene, nitro, and methylsulfonyl. Furthermore, the robustness of this methodology is depicted by the late-stage modification of estrone and synthesis of vortioxetine. Remarkably, synthesis of more challenging organic materials with large ring tension under milder conditions and synthesis of some halogen contained diaryl sulfides which could not be synthesized using metal-catalyzed coupling reactions of aryl halogen are successfully accomplished with this protocol.
- Cao, Fei,Chen, Jinhong,Deng, Jiedan,Deng, Xuemei,Hou, Yongsheng,Shao, Xiangfeng,Shi, Tao,Wang, Yongqiang,Wang, Zhen,Wu, Lingxi,Yang, Jinru,Yang, Yuhang
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p. 2707 - 2712
(2020/03/11)
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- Synthesis and nano-Pd catalyzed chemoselective oxidation of symmetrical and unsymmetrical sulfides
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A highly chemoselective, efficient and nano-Pd catalyzed protocol for the rapid construction of sulfoxides and sulfones via the oxidation of symmetrical and unsymmetrical sulfides using H2O2 as an oxidant has been developed, respectively. The ready availability of starting materials, easy recovery and reutilization of the catalyst, wide substrate scope, and high yields make this protocol an attractive alternative. The process also involves the metal-free and microwave-promoted synthesis of symmetrical diarylsulfides, and FeCl3-mediated preparation of symmetrical diaryldisulfides through the reaction of arenediazonium tetrafluoroborates with Na2S·9H2O as a sulfur source. In addition, unsymmetrical sulfides were generated via the K2CO3-mediated reaction of arenediazonium tetrafluoroborates with symmetrical disulfides.
- Li, Xing,Du, Jia,Zhang, Yongli,Chang, Honghong,Gao, Wenchao,Wei, Wenlong
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p. 3048 - 3055
(2019/03/21)
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- NiFe2O4 as a magnetically recoverable nanocatalyst for odourless C–S bond formation via the cleavage of C–O bond in the presence of S8 under mild and green conditions
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We present green methodologies for one-pot and odourless syntheses of unsymmetric and symmetric diaryl sulfides via C─O bond activation using NiFe2O4 magnetic nanoparticles as a reusable heterogeneous nanocatalyst. The synthesis of unsymmetric sulfides is performed using the cross-coupling reaction of phenolic esters such as acetates, triflates and tosylates with arylboronic acid/S8 or triphenyltin chloride/S8 as thiolating agents in the presence of base and NiFe2O4 magnetic nanoparticles as a catalyst in poly(ethylene glycol) as solvent at 60–85°C. Also, the synthesis of symmetric diaryl sulfides from phenolic compounds using S8 as the sulfur source and NiFe2O4 as catalyst in dimethylformamide at 120°C is described. Using these protocols, the syntheses of various unsymmetric and symmetric sulfides become easier than using the available protocols due to the use of a magnetically reusable bimetallic nanocatalyst and avoiding the use of thiols and aryl halides.
- Atashkar, Bahareh,Rostami, Amin,Rostami, Abed,Zolfigol, Mohammad Ali
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- Copper-Catalyzed Production of Diaryl Sulfides Using Aryl Iodides and a Disilathiane
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A disilathiane was found to be a novel S1 source for the copper-catalyzed synthesis of diaryl sulfides using aryl iodides. The reaction of iodoarenes and hexamethyldisilathiane, (Me 3 Si) 2 S, in the presence of a catalytic amount of CuI/1,10-phenanthroline provided various types of diaryl sulfides in good yields.
- Ogiwara, Yohei,Maeda, Hiromu,Sakai, Norio
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supporting information
p. 655 - 657
(2017/11/29)
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- Cu (II) and Cd (II) anchored functionalized mesoporous SBA-15 as novel, highly efficient and recoverable heterogeneous catalysts for green oxidative coupling of thiols and C–S cross-coupling reaction of aryl halides
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Two novel heterogeneous catalysts have been synthesized by anchoring Cu and Cd Creatinine complexes onto the surface of mesochannels of SBA-15 for highly efficient oxidative coupling of thiols to disulfides using hydrogen peroxide and synthesis of sulfides using S8 and KOH. The structure of the prepared catalysts was determined using SEM, FT-IR, X-ray diffraction, elemental analysis, N2 adsorption–desorption analysis and TGA. The catalysts significantly enhanced the reaction rate of the oxidative coupling of thiols and C–S bond formations. The catalysts were reused several times without appreciable loss in their activity.
- Molaei, Somayeh,Tamoradi, Taiebeh,Ghadermazi, Mohammad,Ghorbani-Choghamarani, Arash
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- Palladium-Catalyzed Enantioselective C?H Olefination of Diaryl Sulfoxides through Parallel Kinetic Resolution and Desymmetrization
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The first example of PdII-catalyzed enantioselective C?H olefination with non-chiral or racemic sulfoxides as directing groups was developed. A variety of chiral diaryl sulfoxides were synthesized with high enantioselectivity (up to 99 %) throu
- Zhu, Yu-Chao,Li, Yan,Zhang, Bo-Chao,Zhang, Feng-Xu,Yang, Yi-Nuo,Wang, Xi-Sheng
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supporting information
p. 5129 - 5133
(2018/03/27)
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- Ligand-free copper-catalysed direct synthesis of diaryl sulfides and diaryl disulfides in wet poly(ethylene glycol)
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An improved protocol has been developed for the one-pot CuI-catalysed preparation of symmetric diaryl sulfides from their available aryl halides in the presence of thiourea as sulfur transfer agent and in the absence of both ligand and organic solvent. This catalytic system was also used for the high-yielding preparation of diaryl disulfides in the presence of C2Cl6 as oxidant.
- Nowrouzi, Najmeh,Abbasi, Mohammad,Latifi, Hadis
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- Copper-Catalyzed C-S Bond Formation via the Cleavage of C-O Bonds in the Presence of S8 as the Sulfur Source
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Useful and applicable methods for one-pot and odorless synthesis of unsymmetrical and symmetrical diaryl sulfides via C-O bond activation are presented. First, a new efficient procedure for the synthesis of unsymmetrical sulfides using the cross-coupling reaction of phenolic esters such as acetates, tosylates, and triflates and with arylboronic acid or triphenyltin chloride as the coupling partners is reported. Depending on the reaction, S 8 /KF or S 8 /NaO t -Bu system is found to be an effective source of sulfur in the presence of copper salts and in poly(ethylene glycol) as a green solvent. Then, the synthesis of symmetrical diaryl sulfides from phenolic compounds by using S 8 as the sulfur source and NaO t -Bu in anhydrous DMF at 120 °C under N 2 is described. By these protocols, the synthesis of a variety of unsymmetrical and symmetrical sulfides become easier than the available protocols in which thiols and aryl halides are directly used for the preparation of the sulfides.
- Rostami, Abed,Rostami, Amin,Ghaderi, Arash,Gholinejad, Mohammad,Gheisarzadeh, Sajedeh
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p. 5025 - 5038
(2017/10/06)
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- A simple, efficient and recyclable catalytic system for carbon-sulfur coupling of aryl halides with thioacetamide
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The carbon-sulfur coupling reaction of aryl halides with thioacetamide using an MCM-41-immobilized bidentate nitrogen copper(I) complex [MCM-41-2N-CuI] as an efficient heterogeneous catalyst is described. Developed catalytic system is found to be effective for the coupling reaction of aryl halides with thioacetamide providing moderate to high yield of diaryl sulfides. This heterogeneous copper catalyst exhibits higher activity than CuI and can be recovered by a simple filtration of the reaction solution and reused for at least 10 consecutive trials without any decreases in activity.
- Cai, Mingzhong,Yao, Ruiya,Chen, Lin,Zhao, Hong
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p. 349 - 354
(2015/01/09)
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- Efficient synthesis of diaryl sulfides by copper-catalysed coupling of aryl halides and thioacetate in water
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A simple economical, and highly efficient catalytic system for the synthesis of diaryl sulfides by a copper-catalysed coupling of aryl halides and thioacetate in water has been developed. A variety of aryl halides reacted with thioacetate to give the desired products in high yields up to 95%. The present catalysis protocol tolerated a wide range of functional groups, including amino, fluoro, and carboxyl moieties.
- Zhang, Yimin,Liu, Li,Chen, Junmin
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- Cu-catalyzed synthesis of diaryl thioethers and S -cycles by reaction of aryl iodides with carbon disulfide in the presence of DBU
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Diaryl thioethers and S-cycles were obtained on the basis of the copper-catalyzed reaction of carbon disulfide and aryl iodides in the presence of DBU. This reaction enables the one-pot synthesis of diaryl thioethers by employing cheap, available, and easy-to-handle carbon disulfide with aryl iodides. The reaction was successfully employed in the construction of sulfur-containing cyclic molecules.
- Zhao, Peng,Yin, Hang,Gao, Hongxin,Xi, Chanjuan
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p. 5001 - 5006
(2013/06/27)
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- Use of base control to provide high selectivity between diaryl thioether and diaryl disulfide for C-S coupling reactions of aryl halides and sulfur and a mechanistic study
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Previous studies have reported that S-arylation produces diaryl disulfide when the precursors include sulfur powder and aryl halide using CuI as the catalyst. However, our research has revealed that the use of different bases in the above S-arylation process results in the coproduction of diarylsulfane and diaryldisulfane. In addition, we have demonstrated that the ratio of the two products can be controlled by selecting the alkalinity of the bases. 1H NMR spectra showed that diaryldisulfane was the first product, which became the reagent in a reaction with aryl halide to form diarylsulfane through CuI catalysis. Various aryl halides were tested to enhance the selectivity between diarylsulfane and diaryldisulfane using various different bases, leading to the following principles. A weak base, such as metal carbonate or acetate, results in the production of only diaryldisulfane; a strong base, such as metal hydroxide, results in the production of both diaryldisulfane and diarylsulfane. According to DFT calculations, hydroxide ions, which were exchanged for iodide and bonded with Cu, affected Cu electrons more strongly to reduce diaryl disulfide.
- Chen, Hsing-Ying,Peng, Wei-Te,Lee, Ying-Hsien,Chang, Yu-Lun,Chen, Yen-Jen,Lai, Yi-Chun,Jheng, Nai-Yuan,Chen, Hsuan-Ying
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p. 5514 - 5522
(2013/11/06)
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- Efficient copper(I)-catalyzed S-arylation of KSCN with aryl halides in PEG-400
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A simple and efficient protocol for CuI-catalyzed C-S bond formation of aryl halides with KSCN to symmetrical diaryl sulfides was reported in PEG-400 without any other additives. A variety of aryl halides were converted to the corresponding diaryl sulfides in good to excellent yields. The present procedure tolerated a variety of functional groups and the steric hindrance of ortho-substituents on aryl halides did not affect the outcome.
- Li, Xiaokang,Yuan, Tangjun,Chen, Junmin
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experimental part
p. 651 - 655
(2012/05/05)
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- Copper-catalyzed direct preparation of diaryl sulfides from aryl iodides using potassium thiocyanate as a sulfur transfer reagent
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A method for direct preparation of diaryl sulfides from aryl iodides using potassium thiocyanate as a sulfur-transfer agent is reported. A catalyst system comprising of a simple copper salt, tetrabutylammonium bromide as a phase-transfer agent and water as the solvent is used. Microwave heating at 200 °C for 60 min allows for the conversion of a range of aryl iodides to the corresponding diaryl sulfides.
- Kelly, Christopher B.,Lee, Christopher Xiang,Leadbeater, Nicholas E.
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experimental part
p. 4587 - 4589
(2011/09/20)
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- REACTION OF DIMETHYL SULFITE WITH PHENYLLITHIUM. FORMATION OF BIPHENYL AND DIPHENYL SULFIDE VIA SULFURANE
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Dimethyl sulfite reacted an excess of phenyllithium yielding biphenyl and diphenyl sulfide in good yield.Other dialkyl sulfites also reacted giving identical yields of biphenyl and diphenyl sulfide irrespective of the structure of the aryl groups, indicating that dialkyl sulfites can be used for the reaction with aryllithiums in place of diaryl sulfoxides.The mechanism of the reaction of diaryl sulfoxides with aryllithium is discussed on the the basis of the isomer distribution of bitolyls, the effect of additives, and the ratio of the benzyne and sulfonium salt pathways.Sulfurane 1 is formed in an initial stage of the reaction of diaryl sulfoxide with aryllithium followed by its competitive collapse by way of benzyne and sulfonium salt pathways.
- Hara, Yoshinori,Matsuda, Minoru
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p. 211 - 222
(2007/10/02)
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