- Synthesis of benzyl thioether derivatives via N-heterocyclic carbene palladium(II)-catalyzed cross coupling of benzylammonium salts with thiophenols
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A new route to benzyl thioether derivatives has been developed via the N-heterocyclic carbene palladium(II)-catalyzed cross coupling of benzylammonium salts with thiophenols. Under the optimal conditions, different benzylammonium salts could be well toler
- Wang, Tao,Guo, Jiarui,Xu, Yongli,Wang, Xiaobo,Wang, Yan,Feng, Dandan,Liu, Lantao
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- Discriminating non-ylidic carbon-sulfur bond cleavages of sulfonium ylides for alkylation and arylation reactions
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A sulfonium ylide participated alkylation and arylation under transition-metal free conditions is described. The disparate reaction pattern allowed the separate activation of non-ylidic S-alkyl and S-aryl bond. Under acidic conditions, sulfonium ylides serve as alkyl cation precursors which facilitate the alkylations. While under alkaline conditions, cleavage of non-ylidic S-aryl bond produces O-arylated compounds efficiently. The robustness of the protocols were established by the excellent compatibility of wide variety of substrates including carbohydrates.
- Fang, Jing,Li, Ting,Ma, Xiang,Sun, Jiuchang,Cai, Lei,Chen, Qi,Liao, Zhiwen,Meng, Lingkui,Zeng, Jing,Wan, Qian
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supporting information
p. 288 - 292
(2021/07/25)
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- Nickel-catalyzed oxidative dehydrogenative coupling of alkane with thiol for C(sp3)-S bond formation
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A nickel-catalyzed oxidative dehydrogenative coupling reaction of alkane with thiol for the construction of C(sp3)-S bond has been established, affording more than 50 alkyl thioethers. Notably, pharmaceutical and agrochemicals, such as Provigil, Chlorbenside and Pyridaben, were readily synthesized by this approach. The sterically hindered ligand BC and disulfide which was formed in situ oxidation of thiol, efficiently avoiding nickel-catalyst poisoning. A set of mechanistic experiments disclose both Ni-catalyzed and Ni-free HAA processes.
- Liu, Shengping,Jin, Shengnan,Wang, Hao,Qi, Zaojuan,Hu, Xiaoxue,Qian, Bo,Huang, Hanmin
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supporting information
(2021/03/15)
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- Methods, Syntheses and Characterization of Diaryl, Aryl Benzyl, and Dibenzyl Sulfides
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Twenty-four aryl benzyl sulfides, diaryl sulfides and dibenzyl sulfides were synthesized by four methods and characterized by 1H NMR, FT-IR and Gas chromatography. The reaction conditions of different synthesis methods were studied from the aspects of time, solvent, base and dispersant. The molecular structures of benzylphenyl sulfide (2S), (4-tert-butylbenzyl)(4-methylphenyl) sulfide (4S), (4-methylbenzyl)(4-methylphenyl) sulfide (9S), di(4-methylphenyl) sulfide (11S), (3,5-dimethylphenyl)(4-methyl phenyl) sulfide (15S), and dibenzyl sulfide (19S) [22] have been determined by single-crystal X-ray crystallography. Compounds 2S and 15S crystallize in the monoclinic space group P21/c, with a = 12.278(3), b = 15.894(3), c = 5.6056(11) ?, β = 94.532(2)°, and Z = 4 for 2S, and a = 9.800(9), b = 7.950(7), c = 16.690(15) ?, β = 100.890(12)°, and Z = 4 for 15S. The unit cell of 4S has a triclinic Pī symmetry with the cell parameters a = 6.0436(10), b = 8.7871(14), c = 15.535(2) ?, α = 81.921(2)°, β = 81.977(2)°, γ = 80.889(2)°, and Z = 2. Compounds 9S and 11S both crystallize in the orthorhombic space group P212121, with a = 6.188(3), b = 8.041(4), c = 26.005(14) ?, and Z = 4 for 9S, and a = 5.835(2), b = 8.010(3), c = 25.131(9) ?, and Z = 4 for 11S. Graphic Abstract: Twenty-four aryl sulfide compounds with different substituents were synthesized and characterized, and the molecular structures of six different sulfide compounds have been determined by single-crystal X-ray crystallography.[Figure not available: see fulltext.]
- Zhou, Wen-Yan,Chen, Min,Zhang, Pei-Zhi,Jia, Ai-Quan,Zhang, Qian-Feng
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p. 301 - 310
(2020/09/07)
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- Synthesis of Aryl Methyl Sulfides from Arysulfonyl Chlorides with Dimethyl Carbonate as the Solvent and C1 Source
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A new procedure for the synthesis of aryl methyl sulfides from dimethyl carbonate (DMC) and arylsulfonyl chlorides has been achieved. In this strategy, DMC plays a dual role as both, C1 building block and green solvent. Arylsulfonyl chlorides served as the sulfur precursors, and a variety of aryl methyl sulfides were obtained in moderate to excellent yields with good functional group tolerance. Additionally, alkylsulfonyl chloride and dibenzyl carbonate are proven to be suitable substrates as well.
- Miao, Ren-Guan,Qi, Xinxin,Wu, Xiao-Feng
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supporting information
p. 5219 - 5221
(2021/10/19)
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- Photocatalytic synthesis method of aryl thioether and derivatives thereof
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The invention belongs to the field of organic synthesis, and particularly relates to a photocatalytic synthesis method of aryl thioether and derivatives thereof. The synthesis method comprises the steps: dissolving an N-(sulfanyl) amide compound into a methyl aromatic compound under the protection of inert gas, and thus obtaining the aryl thioether compound under the action of light, a catalyst, aligand and alkali. According to the method, the coupling reaction of a C-S bond is completed through visible light induction by utilizing a light/Ni dual-catalytic system, so that the method has goodfunctional group compatibility, and the C-S bond compound can be selectively and efficiently constructed in one step. The method has the advantages of simple catalytic system, mild reaction conditions, economical, simple and easily available substrate, simple reaction operation and the like.
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-
Paragraph 0056; 0057; 0058; 0059
(2021/04/03)
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- Unusual Application for Phosphonium Salts and Phosphoranes: Synthesis of Chalcogenides
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A novel strategy for the synthesis of sulfides and selenides from phosphonium salts and thio- or selenesulfonates, commercially available compounds, is described. When phosphoranes were used in the reaction, different products were obtained. The methodology does not require the use of metals, reactive species, or anhydrous conditions to be performed.
- Moura, Igor M. R.,Tranquilino, Arisson,Sátiro, Barbara G.,Silva, Ricardo O.,De Oliveira-Silva, Diogo,Oliveira, Roberta A.,Menezes, Paulo H.
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p. 5954 - 5964
(2021/05/04)
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- Transition-Metal-Free and Base-Promoted Carbon-Heteroatom Bond Formation via C-N Cleavage of Benzyl Ammonium Salts
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A facile and general method for constructing carbon-heteroatom (C-P, C-O, C-S, and C-N) bonds via C-N cleavage of benzyl ammonium salts under transition-metal-free conditions was reported. The combination of t-BuOK and 18-crown-6 enabled a wide range of substituted benzyl ammonium salts to couple readily with different kinds of heteroatom nucleophiles, i.e. hydrogen phosphoryl compounds, alcohols, thiols, and amines. Good functional group tolerance was demonstrated. The scale-up reaction and one-pot synthesis were also successfully performed.
- Liu, Long,Tang, Yuanyuan,Wang, Kunyu,Huang, Tianzeng,Chen, Tieqiao
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p. 4159 - 4170
(2021/03/09)
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- Redox-active benzimidazolium sulfonamides as cationic thiolating reagents for reductive cross-coupling of organic halides
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Redox-active benzimidazolium sulfonamides as thiolating reagents have been developed for reductive C-S bond coupling. The IMDN-SO2R reagent provides a bench-stable cationic precursor to generate a portfolio of highly active N-S intermediates, which can be successfully applied in cross-electrophilic coupling with various organic halides. The employment of an electrophilic sulfur source solved the problem of catalyst deactivation and avoided odorous thiols, featuring practical conditions, broad substrate scope, and excellent tolerance.
- Zhang, Weigang,Huang, Mengjun,Zou, Zhenlei,Wu, Zhengguang,Ni, Shengyang,Kong, Lingyu,Zheng, Youxuan,Wang, Yi,Pan, Yi
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p. 2509 - 2514
(2021/03/01)
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- Synthesis method of benzyl sulfide
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At present, there are many sulfur-containing drugs used for treating various diseases in the market, such as antipsychotic drug chloropropylthiophene; and sulfide has a wide biological activity, and not only can be easily converted into other types of sul
- -
-
Paragraph 0009-0013
(2021/01/12)
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- Unusual Deoxidative Coupling Reaction of β-Sulfinyl Esters with Benzylic Trimethylammonium Salts
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A KOH-promoted unusual deoxidative coupling reaction of β-sulfinyl esters with benzylic trimethylammonium salts to produce thioethers is discovered for the first time. If quaternary ammonium salts synthesized from enantiomerically enriched amines are adopted, highly enantiomerically enriched benzyl thioethers (>95-99% ee) with configurations opposite to those of the enantiomerically enriched amines are obtained.
- Chen, Feng,Feng, Hang,He, Ze,Zeng, Qingle,Zhang, Qiaoling
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p. 7806 - 7812
(2021/06/25)
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- Transition metal-free coupling reactions of benzylic trimethylammonium salts with di(hetero)aryl disulfides and diselenides
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A new protocol was developed to synthesize (enantioenriched) thioethers and selenoethers from (chiral) benzylic trimethylammonium salts and di(hetero)aryl disulfides or diselenides. These syntheses were promoted by the presence of weak base and did not require the use of any transition metal, and resulted in the target products with good to excellent yields (72-94%). Using quaternary ammonium salts synthesized from enantiomerically enriched amines led to highly enantiopure benzylic thioethers and selenoethers (94-99% ee) with configurations reversed from those of their enantioenriched quaternary ammonium salts. This journal is
- Li, Fuhai,Wang, Dan,Chen, Hongyi,He, Ze,Zhou, Lihong,Zeng, Qingle
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p. 13029 - 13032
(2020/11/07)
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- Synthesis of benzyl sulfidesviasubstitution reaction at the sulfur of phosphinic acid thioesters
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An ambident electrophilicity of phosphinic acid thioesters is disclosed. Unexpected carbon-sulfur bond formation took place in the reaction between phosphinic acid thioesters and benzyl Grignard reagents. The developed method for benzyl sulfides has a wide substrate scope and was applicable for the synthesis of a drug analog.
- Nishiyama, Yoshitake,Hosoya, Takamitsu,Yoshida, Suguru
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supporting information
p. 5771 - 5774
(2020/06/03)
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- Preparation method of alkyl sulfide
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The invention relates to a preparation method of alkyl sulfide. The method comprises the following steps: under the protection of nitrogen, sequentially adding transition metal, a nitrogen ligand, a cocatalyst, an oxidant, a solvent, alkane and thiophenol or mercaptan into a reaction tube, carrying out oxidative dehydrogenation coupling reaction at 80-150 DEG C, ending the reaction after 6-48 hours, evaporating the solvent to dryness, and carrying out column chromatography separation to obtain the alkyl sulfide compound. The method is simple in synthesis process, mild in reaction condition, high in yield and easy to industrialize.
- -
-
Paragraph 0043
(2019/12/02)
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- Fe3O4@SiO2-copper sucrose xanthate as a green nanocatalyst for N-, O- and S-arylation
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Formation of C(sp2)–X bonds was carried out using a Fe3O4@SiO2-copper(I) sucrose xanthate nanoparticle catalyst with the aid of the copper(I) xanthate moiety in the catalyst which was prepared from the reaction between sucrose and carbon disulfide through an alkaline medium via the traditional Zeise approach. Various techniques were employed for the characterization of these novel nanoparticles. Three sorts of heteroatoms, N, O and S, successfully underwent heteroatom arylation to produce secondary or tertiary amines, ethers and thioethers, respectively.
- Radfar, Iman,Kazemi Miraki, Maryam,Esfandiary, Naghmeh,Ghandi, Leila,Heydari, Akbar
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- Synthesis method of thioether compounds
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The invention discloses a synthesis method of thioether compounds. The method comprises steps as follows: phosphorus trichloride and a solvent with uniformly distributed sulfoxide compounds are mixeduniformly, after mixing, the mixture is subjected to a reaction at the temperature of 20-25 DEG C for 0.5-6 h, and the thioether compounds are obtained, wherein the solvent is acetonitrile. Compared with the prior art, the synthesis method has the advantages that raw materials are cheap and easy to obtain, a reducer is cheap and easy to obtain and store, and a series of thioether compounds can beobtained.
- -
-
Paragraph 0092-0096
(2019/08/02)
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- Rhodium-Catalyzed C-H/C-H Cross Coupling of Benzylthioethers or Benzylamines with Thiophenes Enabled by Flexible Directing Groups
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Reported herein is an efficient synthetic protocol to ortho-functionalized 2-aryl thiophenes via Rh(III)-catalyzed C-H/C-H cross coupling of benzylthioethers or benzylamines with thiophenes. Both ortho- and meta-substituted benzylthioethers give monoheteroarylated products, while ortho-unhindered substrates mainly provide diheteroarylated benzylthioethers. The C-H/C-H cross coupling of benzylamines with thiophenes exclusively generates diheteroarylated benzaldehydes. Mechanistic investigation discloses a three-step tandem process involving the ortho-C-H diheteroarylation of benzylamine, the oxidation of benzylamine to imine, and the hydrolysis of imine to aldehyde.
- Yang, Shiping,Cheng, Rui,Zhao, Tingxing,Luo, Anping,Lan, Jingbo,You, Jingsong
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supporting information
p. 5086 - 5090
(2019/07/03)
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- Merging Photoredox and Organometallic Catalysts in a Metal–Organic Framework Significantly Boosts Photocatalytic Activities
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Metal–organic frameworks (MOFs) have been extensively used for single-site catalysis and light harvesting, but their application in multicomponent photocatalysis is unexplored. We report here the successful incorporation of an IrIII photoredox catalyst and a NiII cross-coupling catalyst into a stable Zr12 MOF, Zr12-Ir-Ni, to efficiently catalyze C?S bond formation between various aryl iodides and thiols. The proximity of the IrIII and NiII catalytic components to each other (ca. 0.6 nm) in Zr12-Ir-Ni greatly facilitates electron and thiol radical transfers from Ir to Ni centers to reach a turnover number of 38 500, an order of magnitude higher than that of its homogeneous counterpart. This work highlights the opportunity in merging photoredox and organometallic catalysts in MOFs to effect challenging organic transformations.
- Zhu, Yuan-Yuan,Lan, Guangxu,Fan, Yingjie,Veroneau, Samuel S.,Song, Yang,Micheroni, Daniel,Lin, Wenbin
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supporting information
p. 14090 - 14094
(2018/10/15)
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- Deoxygenation of sulphoxides to sulphides with trichlorophosphane
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An efficient route to deoxygenation of sulphoxides to sulphides with PCl3 under mild reaction condition was developed. PCl3 was used as a reducing agent for the first time to convert sulphoxides to sulphides. The mild conditions, use of cheap and readily available reagent, and broad substrate scope render it a useful strategy for preparing sulphides.
- Zhao, Xia,Zheng, Xiancai,Yang, Bo,Sheng, Jianqiao,Lu, Kui
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p. 1200 - 1204
(2018/02/21)
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- Nickel-Catalyzed C?S Bond Formation via Decarbonylative Thioetherification of Esters, Amides and Intramolecular Recombination Fragment Coupling of Thioesters
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A nickel catalyzed cross-coupling protocol for the straightforward C?S bond formation has been developed. Various mercaptans and a wide range of ester and amide substrates bearing various substituents were tolerated in this process which afforded products in good to excellent yields. Furthermore, an intramolecular protocol for the synthesis of thioethers starting from thioesters has been developed. The utility of this protocol has been demonstrated in a new synthetic protocol of benzothiophene.
- Lee, Shao-Chi,Liao, Hsuan-Hung,Chatupheeraphat, Adisak,Rueping, Magnus
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supporting information
p. 3608 - 3612
(2018/03/13)
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- Eco-compatible three component strategies for C-S bond formation in thioether and S-aryl-carbamodithioate compounds catalyzed by copper(II) nanoparticles supported on modified AlPO4
-
One-pot and three components C-S bond formation reactions in thioethers and S-aryl-carbamodithioates have been catalyzed by a copper heterogeneous nano-catalyst supported on modified AlPO4 under different reaction conditions. The above-mentioned nano-catalyst has been characterized by various techniques such as SEM, TEM, AFM, XRD, FT-IR, UV–Vis, CV, BET, TGA, ICP and XPS spectrometry and its particle size was estimated to be between 60–110?nm. Finally, the reusability of the catalyst up to ten cycles without any significant leaching is one of the outstanding properties of the catalyst.
- Sharghi, Hashem,Ghaderi, Iman,Doroodmand, Mohammad Mahdi
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- Efficient dehydrative alkylation of thiols with alcohols catalyzed by alkyl halides
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Alcohols can be efficiently converted into the useful thioethers by a transition metal- and base-free dehydrative S-alkylation reaction with thiols or disulfides by employing alkyl halides as the effective catalyst. This simple and efficient method is a green and practical way for the preparation of thioethers, as it tolerates a wide range of substrates such as aryl and alkyl thiols, as well as benzylic, allylic, secondary, tertiary, and even the less reactive aliphatic alcohols.
- Yang, Yaqi,Ye, Zihang,Zhang, Xu,Zhou, Yipeng,Ma, Xiantao,Cao, Hongen,Li, Huan,Yu, Lei,Xu, Qing
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supporting information
p. 9638 - 9642
(2017/11/30)
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- Metal–organic framework MOF-199-catalyzed direct and one-pot synthesis of thiols, sulfides and disulfides from aryl halides in wet polyethylene glycols (PEG 400)
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A highly porous metal–organic frame work Cu3 BTC2 (copper(II)-benzene-1,3,5-tricarboxylate) that is known as MOF-199 was synthesized from the reaction of 1,3,5-benzenetricarboxylic acid and Cu(OAc)2·H2O by a solvothermal method and characterized by several techniques including FT-IR, XRD, EDX and scanning electron microscopy. The MOF-199 used as an efficient catalyst for one-pot synthesis of thiols by domino reactions of aryl halides and thiourea, and subsequently conversion to aryl alkyl sulfides and diaryl disulfides in polyethylene glycols (PEGs). A variety of aryl alkyl sulfides can be obtained in good to excellent yields in a relatively short reaction time and in the presence of the trace amount of catalyst. Also, the catalyst can be separated from the reaction mixture by decanting, and be reused without significant degradation in catalytic activity.
- Soleiman-Beigi, Mohammad,Sadeghizadeh, Fatemeh,Basereh, Ali
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p. 572 - 583
(2017/09/27)
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- Aryl alkyl, aryl aryl thioether compound and its synthesis method
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The invention discloses a synthesis method of an aryl-alkyl and aryl-aryl thioether compound represented by a formula (III). According to the synthesis method, aryl tetrafluoroboric acid diazonium salt is taken as a reaction raw material in a reaction solvent, aryl and alkyl thiosulfate is taken as a sulfurizing agent, and the materials react under the catalysis action of visible light and a photosensitive agent to obtain the aryl-alkyl and aryl-aryl thioether compound. According to the synthesis method, the raw materials are easy to obtain and are cheap, the reaction operation is simple, the reaction condition is mild and environment-friendly, the yield is higher, the functional group tolerance is excellent, later modification of drugs is successfully realized, and an efficient C-S bond construction method is provided for medicinal chemistry and biological orthogonal chemistry research.
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-
Paragraph 0035-0038
(2017/08/16)
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- Nano cobalt ferrite catalyzed coupling reaction of nitroarene and alkyl halide: An odorless and ligand-free rout to unsymmetrical thioether synthesis
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This study describes an odorless protocol for the synthesis of unsymmetrical sulfides via cobalt ferrite (CoFe2O4) catalyzed cross-coupling reaction of nitroarenes with alkyl halides in the presence of thiourea as sulfur source under
- Moghaddam, Firouz Matloubi,Pourkaveh, Raheleh
-
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- Nature of the copper-oxide-mediated C-S cross-coupling reaction: Leaching of catalytically active species from the metal oxide surface
-
Copper-oxide-catalyzed cross-coupling reaction is a well-known strategy in heterogeneous catalysis. A large number of applications have been developed, and catalytic cycles have been proposed based on the involvement of the copper oxide surface. In the present work, we have demonstrated that copper(I) and copper(II) oxides served as precursors in the coupling reaction between thiols and aryl halides, while catalytically active species were formed upon unusual leaching from the oxide surface. A powerful cryo-SEM technique has been utilized to characterize the solution-state catalytic system by electron microscopy. A series of different experimental methods were used to reveal the key role of copper thiolate intermediates in the studied catalytic reaction. The present study shows an example of leaching from a metal oxide surface, where the leaching process involved the formation of a metal thiolate and the release of water. A new synthetic approach was developed, and many functionalized sulfides were synthesized with yields of up to 96%, using the copper thiolate catalyst. The study suggests that metal oxides may not act as an innocent material under reaction conditions; rather, they may represent a source of reactive species for solution-state homogeneous catalysis.
- Panova, Yulia S.,Kashin, Alexey S.,Vorobev, Maxim G.,Degtyareva, Evgeniya S.,Ananikov, Valentine P.
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p. 3637 - 3643
(2016/07/06)
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- Photoredox Mediated Nickel Catalyzed Cross-Coupling of Thiols with Aryl and Heteroaryl Iodides via Thiyl Radicals
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Ni-catalyzed cross-couplings of aryl, benzyl, and alkyl thiols with aryl and heteroaryl iodides were accomplished in the presence of an Ir-photoredox catalyst. Highly chemoselective C-S cross-coupling was achieved versus competitive C-O and C-N cross-couplings. This C-S cross-coupling method exhibits remarkable functional group tolerance, and the reactions can be carried out in the presence of molecular oxygen. Mechanistic investigations indicated that the reaction proceeded through transient Ni(I)-species and thiyl radicals. Distinct from nickel-catalyzed cross-coupling reactions involving carbon-centered radicals, control experiments and spectroscopic studies suggest that this C-S cross-coupling reaction does not involve a Ni(0)-species.
- Oderinde, Martins S.,Frenette, Mathieu,Robbins, Daniel W.,Aquila, Brian,Johannes, Jeffrey W.
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supporting information
p. 1760 - 1763
(2016/03/01)
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- Aryl-aryl, aryl-alkyl, alkyl-alkyl asymmetric the sulfur compounds and its synthetic method
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The invention discloses a synthesis method of aryl-aryl, aryl-alkyl and alkyl-alkyl asymmetric persulfides as shown in a formula (II) or a formula (IV). According to the synthesis method, with sulfinic acid sodium salt, and halogenated hydrocarbon and Na2S2O3 as reaction materials or Bunte salt as a reaction material instead of the halogenated hydrocarbon and Na2S2O3, the aryl-aryl, aryl-alkyl and alkyl-alkyl asymmetric persulfides are obtained by reaction in the absence of transition metal. The synthesis method has the advantages that the reaction is efficient; the yield is high; a vulcanizing reagent is cheap, easily available, stable, and free of pungent smell; no strong acid or alkali or extra oxidizing or reducing agent is added in reaction; the condition is relatively mild; and no transition metal is used as a catalyst in the reaction, and therefore the method is economical, practical and friendly to the environment; a reaction substrate is easy to prepare; the reaction efficiency is high after the reaction is amplified, and therefore, the synthesis method has a wide application prospect and practical value.
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-
Paragraph 0240-0243
(2016/11/17)
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- Functionalized graphene oxide as an efficient adsorbent for CO2 capture and support for heterogeneous catalysis
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We have designed new imine-functionalized graphene oxide (IFGO) through post synthetic modifications involving co-condensation of 3-aminopropyltriethoxysilane with graphene oxide basal plane containing hydroxyl and epoxy functional groups, followed by Schiff base condensation reaction with 2,6-diformyl-4-methylphenol and impregnation of copper(ii) to it through covalent attachment (Cu-IFGO). Powder X-ray diffraction, N2 sorption analysis, FT-IR, HR-TEM, FE-SEM and TGA/DTA analysis are employed to characterize the materials. The IFGO material exhibits good CO2 storage capacity of 8.10 mmol g-1 (35.64 wt%) and 2.10 mmol g-1 (9.24 wt%) at 273 K and 298 K temperature, respectively, up to 3 bar pressure, suggesting its potential application in environmental clean-up. Also, Cu-IFGO showed high catalytic activity in microwave-assisted one-pot three-component C-S coupling reactions for a diverse range of aryl halides with thiourea and benzyl bromide in aqueous medium to obtain aryl thioether products (maximum yield 86%), which are derivatives of natural products. Moreover, having imine and hydroxyl groups in functionalized graphene oxide, the grafted Cu(ii) chelated at the graphene oxide surface so strongly that it could not be leached out from the material during the course of the coupling reaction. Thus, it displayed very small decrease in product yield up to the sixth reaction cycle suggesting a sustainable future of this Cu(ii)-grafted catalyst.
- Bhanja, Piyali,Das, Sabuj Kanti,Patra, Astam K.,Bhaumik, Asim
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p. 72055 - 72068
(2016/08/09)
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- A new Cu-anchored mesoporous organosilica material for facile C-S coupling reactions under microwave irradiation
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We report a new ordered Cu-anchored 2D-hexagonal mesoporous imine functionalized organosilica material Cu-MPIOS. This Cu-anchored mesoporous material has been synthesized via post synthetic functionalization of SBA-15 with 3-(2-aminoethylamino)propyl-dimethoxymethylsilane followed by Schiff-base condensation with 2-thiophene carboxaldehyde. Cu(I) has been grafted finally over Schiff-base functionalized mesoporous material through chemical impregnation to obtain Cu-MPIOS. The materials are characterized thoroughly using various techniques like powder X-ray diffraction, N2 adsorption/desorption analysis, FTIR, UV-vis spectroscopy, FEG-TEM, FE-SEM, 13C cross-polarization magic angle spinning NMR, TGA/DTA, EPR, AAS and CHN chemical analysis. High Brunauer-Emmett-Teller (BET) surface area and the presence of very large size mesopores (8.1 nm) in Cu-MPIOS has motivated us to explore its catalytic activity in one-pot three-component C-S cross coupling reaction by varying different aryl halides in the aqueous medium under microwave assisted heating conditions. This heterogeneous Cu-catalyst shows high catalytic performance as well as good recycling efficiency in this C-S coupling reaction, suggesting its future potential for the synthesis of value added thioether derivatives.
- Bhanja, Piyali,Gomes, Ruth,Satyanarayana, Lanka,Bhaumik, Asim
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p. 104 - 112
(2016/02/18)
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- Benign and efficient preparation of thioethers by solvent-free S-alkylation of thiols with alkyl halides catalyzed by potassium fluoride on alumina
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The preparation of thioethers by S-alkylation of various thiols with alkyl halides under solvent-free reaction conditions using potassium fluoride on alumina (KF/Al2O3) as a solid catalyst has been investigated in detail with respect to three different modes of reaction activation (ultrasound irradiation, microwave irradiation, and conventional heating) for obtaining maximum yield of the thioether. The importance of KF/Al2O3 as a particularly efficient catalyst was corroborated for all three modes of reaction activation, although the reaction time was found to be strongly dependent on the mode of activation. The yield of the thioethers was also found to depend on the amount of the solid catalyst relative to the equimolar amounts of the two reactants.
- Nguyen, Kha Ngoc,Duus, Fritz,Luu, Thi Xuan Thi
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p. 349 - 360
(2016/06/01)
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- Indium-Catalyzed Reductive Sulfidation of Esters by Using Thiols: An Approach to the Diverse Synthesis of Sulfides
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A new reductive preparation of unsymmetrical sulfides from esters and thiols in the presence of InI3 and either 1,1,3,3-tetramethyldisiloxane (TMDS) or PhSiH3 as the reductant was developed. This protocol was applied to not only benzoic acid esters that have a methoxy, methyl, chloro, bromo, iodo, or trifluoromethyl group on the aromatic ring but also aliphatic acid esters with either aromatic or aliphatic thiols. A reaction mechanism is proposed by using Hammett plot results and several control experiments. The reductive preparation of unsymmetrical sulfides from esters and thiols by using InI3 and either 1,1,3,3-tetramethyldisiloxane (TMDS) or PhSiH3 was developed. Several mechanistic studies support that the present transformation proceeds through O,S-and S,S-acetals as the reaction intermediates. TMDS = 1,1,3,3-tetramethyldisiloxane, R = aliphatic group.
- Miyazaki, Takahiro,Kasai, Shinsei,Ogiwara, Yohei,Sakai, Norio
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p. 1043 - 1049
(2016/03/01)
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- Mechanistic Study of a Photocatalyzed C-S Bond Formation Involving Alkyl/Aryl Thiosulfate
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This study presents thioether construction involving alkyl/aryl thiosulfates and diazonium salt catalyzed by visible-light-excited [Ru(bpy)3Cl2] at room temperature in 44-86 % yield. Electron paramagnetic resonance studies found that thiosulfate radical formation was promoted by K2CO3. Conversely, radicals generated from BnSH or BnSSBn (Bn=benzyl) were clearly suppressed, demonstrating the special property of thiosulfate in this system. Transient absorption spectra confirmed the electron-transfer process between [Ru(bpy)3Cl2] and 4-MeO-phenyl diazonium salt, which occurred with a rate constant of 1.69×109 M-1 s-1. The corresponding radical trapping product was confirmed by X-ray diffraction. The full reaction mechanism was determined together with emission quenching data. Furthermore, this system efficiently avoided the over-oxidation of sulfide caused by H2O in the photoexcited system containing Ru2+. Both aryl and heteroaryl diazonium salts with various electronic properties were investigated for synthetic compatibility. Both alkyl- and aryl-substituted thiosulfates could be used as substrates. Notably, pharmaceutical derivatives afforded late-stage sulfuration smoothly under mild conditions.
- Li, Yiming,Xie, Weisi,Jiang, Xuefeng
-
supporting information
p. 16059 - 16065
(2015/11/03)
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- Microwave-Assisted Copper-Catalyzed Cross-Coupling Reaction of Thiols with Aryl Iodides in Water
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Microwave-promoted C-S bond formation from thiols and aryl iodides in the presence of a copper catalyst is reported. A combination of copper(II) oxide and 1,10-phenanthroline catalyzes this reaction. A variety of aryl iodides react smoothly with thiols to provide the corresponding aryl sulfides in good to excellent yields. Notably, the reactions proceed in water with a short reaction time (30 minutes). This system shows broad functional-group tolerance; amino, chloro, bromo, acetyl, and nitro groups are unaffected by the reaction conditions.
- Chen, Yi-An,Badsara, Satpal Singh,Tsai, Wan-Ting,Lee, Chin-Fa
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p. 181 - 186
(2015/05/04)
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- Efficient reduction of sulfoxides with NaHSO3 catalyzed by I2
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An efficient method for the deoxygenation of sulfoxides into their corresponding sulfides at room temperature using NaHSO3 in the presence of catalytic I2 has been reported.
- Abbasi, Mohammad,Mohammadizadeh, Mohammad Reza,Moradi, Zahra
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p. 6610 - 6613
(2015/11/09)
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- One-Pot Copper-Catalysed Thioetherification of Aryl Halides Using Alcohols and Lawesson's Reagent in Diglyme
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A new protocol for the thioetherification of structurally varied alcohols with aryl halides using Lawesson's reagent, catalysed by copper(I) iodide, and using diglyme as a safe solvent was developed. Using this method, the reactions of aryl halides proceeded efficiently, and the desired sulfides were obtained in high to excellent yields. The method uses alcohols as starting materials, which is a significant advantage over methods that start from thiols. Alcohols are widely commercially available in a much greater structural diversity than thiols, and they are also nontoxic and not foul-smelling. A reaction mechanism was proposed. A copper-catalysed method for the thioetherification of alcohols with aryl halides using Lawesson's reagent was developed.
- Gholinejad, Mohammad
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p. 4162 - 4167
(2015/06/30)
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- Ligand-free Cu-catalyzed odorless synthesis of unsymmetrical sulfides through cross-coupling reaction of aryl/benzyl/alkyl halides with an aryl boronic acid/S8 system as a thiolating agent in PEG
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In this article, we have presented a novel, efficient and environmentally benign method for one-pot, one-step and odorless synthesis of a wide range of unsymmetrical sulfides from the reaction of aryl/benzyl/alkyl halides with aryl boronic acids in the presence of S8, NaOH and a catalytic amount of CuI in PEG200 as green solvent at 40-60 °C. The products were obtained in moderate to excellent yields. More importantly, this reaction is applicable for the gram-scale preparation of the desired sulfides.
- Rostami, Amin,Rostami, Abed,Ghaderi, Arash,Zolfigol, Mohammad Ali
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p. 37060 - 37065
(2015/05/05)
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- Sulfide synthesis through copper-catalyzed C-S bond formation under biomolecule-compatible conditions
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We report here an efficient and mild method for constructing C-S bonds. The reactions were carried out with Na2S2O3 as a sulfurating reagent, CuSO4 as a catalyst, and water as solvent without any surfactant. The products were achieved in moderate to excellent yields at room temperature under air. Notably, this reaction is compatible with various biomolecules including amino acids, oligosaccharides, nucleosides, proteins, and cell lysates. This journal is
- Zhang, Yonghong,Li, Yiming,Zhang, Xiaomei,Jiang, Xuefeng
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p. 941 - 944
(2015/01/09)
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- A highly efficient heterogeneous rhodium(I)-catalyzed C-S coupling reaction of thiols with polychloroalkanes or alkyl halides under mild conditions
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Heterogeneous C-S coupling reaction of thiols with polychloroalkanes or alkyl halides was achieved at 30 or 80 °C in the presence of 5 mol% of an MCM-41-immobilized bidentate phosphine rhodium complex (MCM-41-2P-RhCl(PPh3)) and triethylamine, yielding a variety of formaldehyde dithioacetals, ethylenedithioethers and unsymmetric thioethers in good to excellent yields. This heterogeneous rhodium catalyst can be easily recovered and recycled by simple filtration of the reaction solution and used for at least 10 consecutive trials without significant loss of activity.
- Xia, Jianhui,Yao, Ruiya,Cai, Mingzhong
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p. 221 - 225
(2015/03/30)
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- Photosensitized oxidation of aryl benzyl sulfoxides. Evidence for nucleophilic assistance to the c-s bond cleavage of aryl benzyl sulfoxide radical cations
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The radical cations of a series of aryl benzyl sulfoxides (4-X-C6H4CH2SOC6H4Y+?) have been generated by photochemical oxidation of the parent sulfoxides sensitized by 3-cyano-N-methylquinolinium perchlorate (3-CN-NMQ+ClO4-). Steady-state photolysis experiments showed the prevailing formation of benzylic products deriving from the C-S fragmentation in the radical cations, together with sulfur-containing products. Formation of sulfoxide radical cations was unequivocally established by laser flash photolysis experiments showing the absorption bands of 3-CN-NMQ? (λmax = 390 nm) and of the radical cations (λmax = 500-620 nm). The decay rate constants of radical cations, determined by LFP experiments, decrease by increasing the electron-donating power of the arylsulfinyl Y substituent and to a smaller extent by increasing the electron-withdrawing power of the benzylic X substituent. A solvent nucleophilic assistance to the C-S bond cleavage has been suggested, supported by the comparison of substituent effects on the same process occurring in aryl tert-butyl sulfoxide radical cations. DFT calculations, performed to determine the bond dissociation free energy in the radical cations, the transition state energies associated with the unimolecular C-S bond cleavage, and the charge and spin delocalized on their structures, were also useful to endorse the nucleophilic assistance to the C-S scission.
- Del Giacco, Tiziana,Lanzalunga, Osvaldo,Lapi, Andrea,Mazzonna, Marco,Mencarelli, Paolo
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p. 2310 - 2318
(2015/09/08)
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- I2-catalyzed oxidative C(sp3)-H/S-H coupling: Utilizing alkanes and mercaptans as the nucleophiles
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By using alkanes and mercaptans as the nucleophiles with di-tert-butyl peroxide (DTBP) as the oxidant, I2-catalyzed oxidative C(sp3)-H/S-H coupling was achieved. This protocol provides a novel process to construct C(sp3)-S bonds from commercially available hydrocarbons and mercaptans.
- Yuan, Jiwen,Ma, Xu,Yi, Hong,Liu, Chao,Lei, Aiwen
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supporting information
p. 14386 - 14389
(2014/12/11)
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- Selective approach to thioesters and thioethers via sp3 C-H activation of methylarenes
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Novel C-S cross-dehydrogenative coupling (CDC) approaches for the selective synthesis of thioesters and thioethers have been developed via sp3 C-H activation of methylarenes and subsequent functionalization. The reaction of methylarenes with thiols resulted in thioesters in the presence of a FeBr2/TBHP system, while treatment of methylarenes with thiols in the Pd(OAc)2/O2/TBHP system led to the formation of thioethers. Both the green protocols demonstrate good functional group tolerance and satisfactory yields. This journal is
- Feng,Lu,Cai
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p. 54409 - 54415
(2015/01/16)
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- Synthesis and characterization of magnetic copper ferrite nanoparticles and their catalytic performance in one-pot odorless carbon-sulfur bond formation reactions
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In this article, we have introduced catalytic application of copper ferrite nanoparticles (CuFe2O4) for one-pot odorless production of aryl alkyl thioethers using thiourea and alkyl bromides in wet polyethylene glycol as a green solvent. The catalyst was also successfully applied for one-pot synthesis of symmetrical diaryl trithiocarbonates via the reaction of sodium sulfide, carbon disulfide and aryl iodides under heterogeneous reaction condition. Magnetic copper ferrite nanoparticles were synthesized using iron (III) chloride and copper (II) chloride, and characterized using XRD, FT-IR, AAS, and TEM analysis. The catalyst was recycled using simple magnetic separation and reused for the five consecutive runs in the reaction of iodobenzene, thiourea and benzyl bromide without appreciable loss of activity.
- Gholinejad, Mohammad,Karimi, Babak,Mansouri, Fariborz
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- A novel method for the reduction of sulfoxides with the N, N, N g, N g-tetrabromobenzene-1,3-disulfonamide (TBBDA)/PPh3 system
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A new method is described for the reduction of sulfoxides to sulfides using N,N,N',N'-tetrabromobenzene-1,3-disulfonamide [TBBDA] in combination with triphenylphosphine. Good to excellent yields, short reaction times, high efficiency and facile isolation of the desired products are the advantages of this method.
- Ghorbani-Vaghei, Ramin,Shiri, Lotfi,Ghorbani-Choghamarani, Arash
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p. 1002 - 1006
(2014/12/10)
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- A highly efficient Cu-catalyzed S-transfer reaction: From amine to sulfide
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A highly efficient Cu-catalyzed dual C-S bonds formation reaction, proceeding in alcohol and water under air, is reported, in which inodorous stable Na2S2O3 is used as a sulfurating reagent. This powerful strategy provides a practical and efficient approach to construct thioethers, using readily available aromatic amines and alkyl halides as starting materials. Sensitive and synthetic useful functional groups could be tolerated. Furthermore, pharmaceuticals, glucose, an amino acid, and a chiral ligand are successfully furnished by this late-stage sulfuration strategy.
- Li, Yiming,Pu, Jiahua,Jiang, Xuefeng
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supporting information
p. 2692 - 2695
(2014/06/09)
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- One-pot synthesis of aryl alkyl thioethers and diaryl disulfides using carbon disulfide as a sulfur surrogate in the presence of diethylamine catalyzed by copper(I) iodide in polyethylene glycol (PEG200)
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A copper catalyzed one-pot protocol for the preparation of aryl alkyl thioethers and diaryl disulfides using carbon disulfide as the sulfur source and diethylamine in polyethylene glycol (PEG200) is described.
- Firouzabadi, Habib,Iranpoor, Nasser,Samadi, Arash
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p. 1212 - 1217
(2014/02/14)
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- Cu-grafted functionalized mesoporous SBA-15: A novel heterogeneous catalyst for facile one-pot three-component C-S cross-coupling reaction of aryl halides in water
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A highly ordered 2D hexagonal Cu-grafted functionalized mesoporous SBA-15 (Cu-PIF-SBA-15) has been designed through postsynthetic modification of mesoporous SBA-15. Surface functionalization technique has been employed to synthesize-NH2 functionalized mesoporous SBA-15 material. Schiff base condensation of this-NH2 functionalized SBA-15 with phloroglucinol dialdehyde leads to the formation of PIF-SBA-15. Reaction of PIF-SBA-15 with Cu(OAc)2·H2O in ethanol under reflux leads to the formation of Cu-PIF-SBA-15 catalyst. This Cu-PIF-SBA-15 catalyst exhibits excellent catalytic activity in a one-pot three-component C-S coupling reaction for a diverse range of aryl halides (bromide and chloride) with thiourea and benzyl bromide in aqueous medium to offer aryl alkyl thioether in very good yields. Due to the strong binding ability of the imine-N and phenolic-OH functional groups present in the phloroglucinol diimine moiety of the framework, the anchored Cu(II) could not leach out from the surface of the mesoporous catalyst during the course of reaction, and it has been observed that six repetitive reaction cycles could not cause any appreciable loss in the catalytic activity of this material.
- Mondal, John,Borah, Parijat,Modak, Arindam,Zhao, Yanli,Bhaumik, Asim
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p. 257 - 265
(2014/05/20)
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- Palladium(II)-catalyzed ortho -olefination of arenes applying sulfoxides as remote directing groups
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A novel palladium-catalyzed ortho-C(sp2)-H olefination protocol has been developed by the use of sulfoxide as the directing group. Importantly, relatively remote coordination can be accessed to achieve the ortho olefination of benzyl, 2-arylethyl, and 3-arylpropenyl sulfoxide substrates, and the olefinated sulfoxide can be easily transformed to other functionalities.
- Wang, Binjie,Shen, Chuang,Yao, Jinzhong,Yin, Hong,Zhang, Yuhong
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supporting information
p. 46 - 49
(2014/01/23)
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- Synthesis of sulfur-bridged polycycles via Pd-catalyzed dehydrogenative cyclization
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A general approach to sulfur-bridged polycycles by palladium-catalyzed double C(sp2)-H bond oxidative cyclization is presented. This protocol afforded diverse sulfur-bridged five-, six-, and seven-membered polycycles in moderate to good yields with a tolerance for a wide variety of functional groups. A sulfide-bridged six-membered pyrene-thienoacene compound was synthesized readily using this method, and excellent performance for photoluminescence quantum yield was observed.
- Wang, Binjie,Liu, Yue,Lin, Cong,Xu, Yiming,Liu, Zhanxiang,Zhang, Yuhong
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supporting information
p. 4574 - 4577
(2015/01/08)
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- Nickel-Schiff base complex catalyzed C-S cross-coupling of thiols with organic chlorides
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We report an efficient, mild and convenient synthetic protocol for the C-S cross-coupling reaction of various aryl, benzyl, allyl chlorides and thiols using 5 mol % Nickel-Schiff base catalyst with NaOH as the base, in DMF at 70 °C. Using this protocol, we have shown that a variety of aryl sulfides can be synthesized in excellent yields from readily available organic chlorides and thiols.
- Gogoi, Prasanta,Hazarika, Sukanya,Sarma, Manas J.,Sarma, Kuladip,Barman, Pranjit
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p. 7484 - 7489
(2014/12/10)
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