- Paired Electrolysis Enabled Ni-Catalyzed Unconventional Cascade Reductive Thiolation Using Sulfinates
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Herein, we have reported a nickel-catalyzed cascade reductive thiolation of aryl halides with sulfinates driven by paired electrolysis. This protocol uses sulfinates as the sulfur source, and various thioethers could be synthesized under mild conditions. By mechanism exploration, we find that a cascade chemical step is allowed on the electrode interface and could alter the reaction pathway in paired electrolysis, whose findings could help the discovery of novel cascade reactions with unique reactivity.
- Kang, Jun-Chen,Li, Zi-Hao,Chen, Chao,Dong, Li-Kun,Zhang, Shu-Yu
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supporting information
p. 15326 - 15334
(2021/10/25)
-
- Nickel-Catalyzed Decarbonylative Thioetherification of Acyl Fluorides via C-F Bond Activation
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Nickel-catalyzed decarbonylative thioetherification of acyl fluorides has been developed. This transformation allows an array of acyl fluorides to react with thiophenols. A wide range of functional groups are well tolerated and the corresponding sulfides can be obtained in good to excellent yields. This protocol provides the formation of diverse carbon-sulfur bonds via a highly efficient decarbonylative process.
- You, Jingwen,Chen, Qiang,Nishihara, Yasushi
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supporting information
p. 3045 - 3050
(2021/05/31)
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- Scalable electrochemical reduction of sulfoxides to sulfides
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A scalable reduction of sulfoxides to sulfides in a sustainable way remains an unmet challenge. This report discloses an electrochemical reduction of sulfoxides on a large scale (>10 g) under mild reaction conditions. Sulfoxides are activated using a substoichiometric amount of the Lewis acid AlCl3, which could be regeneratedviaa combination of inexpensive aluminum anode with chloride anion. This deoxygenation process features a broad substrate scope, including acid-labile substrates and drug molecules.
- Kong, Zhenshuo,Pan, Chao,Li, Ming,Wen, Lirong,Guo, Weisi
-
supporting information
p. 2773 - 2777
(2021/04/21)
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- A template free protocol for fabrication of a Ni(ii)-loaded magnetically separable nanoreactor scaffold for confined synthesis of unsymmetrical diaryl sulfides in water
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In the present report, an environmentally benign magnetically recoverable nickel(ii)-based nanoreactor as a heterogeneous catalyst has been developedviaa template free approach. The catalytic performance of the synthesized catalyst is assessed in the confined oxidative coupling of arenethiols with arylhydrazines to form unsymmetrical diaryl sulfides under aerobic conditions. The salient features of our protocol include oxidant- and ligand-free conditions, use of water as a green solvent, room temperature and formation of nitrogen and water as the only by-products. Moreover, a broad range of functional groups are tolerated well and provide the corresponding diaryl sulfides in moderate to good yields. Moreover, the heterogeneous nature of the catalyst permits facile magnetic recovery and reusability for up to seven runs, making the present protocol highly desirable from industrial and environmental standpoints.
- Arora, Gunjan,Gaur, Rashmi,Gupta, Radhika,Rana, Pooja,Sharma, Rakesh Kumar,Yadav, Manavi,Yadav, Priya
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p. 19390 - 19396
(2020/06/04)
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- Copper(II)-faciliated synthesis of substituted thioethers and 5-substituted 1H-tetrazoles: Experimental and theoretical studies
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Benzoylhydrazine based Schiff base-ligated two new copper(II) complexes, [Cu(L1)2] (1) and [Cu(L2)2] (2) were synthesized by the reaction of Cu(CH3COO)2·H2O with respective Schiff base ligand 1-[(4-nitrophenyl)ethylidene] benzohydrazide (HL1) or 1-[(4-methoxyphenyl)ethylidene] benzohydrazide (HL2). Both complexes were isolated as greenish solid and fully characterized by elemental analysis, FT-IR, EPR, thermo-gravimetric (TG) analysis and Cyclic Voltammetry. The molecular structures of both complexes have also been determined by single crystal X-ray crystallography, which confirmed the coordination of Schiff base ligands through N, O donor atoms and distorted square planar geometry around the Cu(II) ion. Both complexes were found to be good homogeneous catalysts for the synthesis of a wide range of substituted thioethers and 5-substituted 1H-tetrazoles in 92% and 93% yield, respectively, at a low catalyst loading (0.5 mol%). The bond angles and distances, as discerned from the DFT calculations, commusurated with the experimental findings. The energy difference between the HOMO and the LUMO, calculated from DFT studies, was found to be 5.645 eV and 6.459 eV for complex 1 and complex 2, respectively. These results are in harmony with the observed higher catalytic activity of complex 1.
- Layek, Samaresh,Agrahari, Bhumika,Dey, Shuvankar,Ganguly, Rakesh,Pathak, Devendra D.
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p. 194 - 206
(2019/06/24)
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- C-S cross-coupling reaction using novel and green synthesized CuO nanoparticles assisted by Euphorbia maculata extract
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In the present study, biosynthesis of CuO nanoparticles using a rapid, eco-friendly, cost-effective and efficient method has been reported employing aqueous Euphorbia maculata extract as mild, renewable and non-toxic reducing and capping agents without adding any surfactants. The biogenic and green method has some benefits compared to conventional physical and chemical methods. It is simple, cheap and environmentally friendly. The biosynthesized CuO NP displayed a color change pattern (from sky blue to black) on preparation and presented its respective broad peak at 365?nm, which was analyzed by UV–Vis spectroscopy. Using the FT-IR analysis, biomolecules in E. maculata extract which are responsible for bioreduction activity and synthesize of CuO NP, were identified. The XRD, EDX and FESEM results confirmed the successful synthesis of CuO nanoparticles of 18?nm sizes, with spherical and sponge crystal structure. The catalytic activity of biosynthesized CuO NPs was studied in C-S cross-coupling reaction. This method has the advantages of high yields, easy work-up, and simple reusability. The recovered CuO NP can be reused four times without any considerable loss of its catalytic activity.
- Alinezhad, Heshmatollah,Pakzad, Khatereh
-
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- CoII immobilized on an aminated magnetic metal-organic framework catalyzed C-N and C-S bond forming reactions: A journey for the mild and efficient synthesis of arylamines and arylsulfides
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In this work, we report a simple and versatile method for the modification of a metal-organic framework (NH2-MIL53(Al)) in a step-wise manner. To characterize the synthesized nanostructured catalyst, a variety of spectroscopic and microscopic techniques including FT-IR, XRD, BET, TEM, FE-SEM, EDX, EDX-mapping, TGA, XPS, VSM, ICP-OES and CHN have been employed. Fe3O4@AMCA-MIL53(Al)-NH2-CoII NPs, which benefit from small nanocrystalline size (10-30 nm, according to the XRD and TEM data) in combination with the coexistence of magnetic nanoparticles, a metal-organic framework, and cobalt species, were found to be an excellent environment catalyst to promote the C-N and C-S cross coupling reactions. A wide range of functional substrates including electron-withdrawing and electron-donating aryl halides underwent the coupling reaction with aromatic/heteroaromatic/benzylic and aliphatic amines and sulfides. The results demonstrated that the yields of the target products were good to excellent and the catalyst can be recycled for at least seven recycling runs without a discernible decrease in its catalytic activity. Furthermore, the heterogeneity studies (such as hot filtration and poisoning tests) efficiently confirmed that the as-synthesized nanostructured catalyst is heterogeneous and completely stable under the reaction conditions. We hope that our study inspires more interest in designing novel catalysts based on using low-cost metal ions (such as cobalt) in the field of cross coupling reactions.
- Mohammadinezhad, Arezou,Akhlaghinia, Batool
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p. 15525 - 15538
(2019/10/19)
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- MOF nano porous-supported C-S cross coupling through one-pot post-synthetic modification
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UIO-66-NH2-Fu?Ni has been synthesized by anchoring a molecular nickel furfural (Fu) complex into a functionalized nanoporous metal-organic framework (MOF) with the amine functional groups, using the one-pot post-synthetic modification. This new
- Alinezhad, Heshmatollah,Ghasemi, Shahram,Cheraghian, Mansoureh
-
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- Nickel-Catalyzed Thiolation of Aryl Halides and Heteroaryl Halides through Electrochemistry
-
Transition-metal-catalyzed coupling reactions are useful tools for synthesizing aryl sulfur compounds. However, conventional transition-metal-catalyzed thiolation of aryl bromides and chlorides typically requires the use of strong base under elevated reaction temperature. Herein, we report the first examples of nickel-catalyzed electrochemical thiolation of aryl bromides and chlorides in the absence of an external base at room temperature using undivided electrochemical cells.
- Liu, Dong,Ma, Hong-Xing,Fang, Ping,Mei, Tian-Sheng
-
supporting information
p. 5033 - 5037
(2019/03/13)
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- Metal-Free Cercosporin-Photocatalyzed C-S Coupling for the Selective Synthesis of Aryl Sulfides under Mild Conditions
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Aryl sulfides are important motifs of bioactive molecules, which are generally synthesized by transition metal-based coupling reactions under harsh conditions. Herein, we developed a new method that visible light along with cercosporin, produced by liquid fermentation and functioned as a cost-effective and environmentally friendly photocatalyst, prompted the selective synthesis of aryl sulfides through C–S coupling of thiols and diazonium salts under mild conditions. Furthermore, this method can also be performed with a great conversion by the direct use of cercosporin-containing fermentation supernatant as catalytic system without organic solvent extraction.
- Li, Jia,Bao, Wenhao,Zhang, Yan,Rao, Yijian
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supporting information
p. 7175 - 7178
(2019/11/16)
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- Preparation method of aromatic thioether compound
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The invention discloses a preparation method of an aromatic thioether compound, belonging to the technical field of catalysis. The invention provides a novel environment-friendly method for efficiently synthesizing a thioether derivative; and under the action of a catalyst, thiophenol and an aryl diazonium salt compound are directly coupled under illumination to generate the aromatic thioether compound, wherein the catalyst is cephalosporin. According to the method disclosed by the invention, the cephalosporin is used as the catalyst; catalytic conditions are mild, and the method can be carried out at room temperature under visible light irradiation; the catalytic activity of the catalyst is high, and the thioether compound can be catalytically synthesized with high selectivity; and the yield of the thioether compound can reach 96% or above by virtue of a trace amount of the catalyst. The photocatalyst disclosed by the invention has the advantages of usage of simple and easily available substrate raw materials, environmental friendliness, low cost and very good application prospect, and can be produced on a large scale.
- -
-
Paragraph 0047-0048
(2019/12/25)
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- Aryldithiocarbamates as thiol alternatives in Cu-catalyzed C(aryl)-S coupling reactions using aryldiazonium tetrafluoroborate salts
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An efficient method for the synthesis of unsymmetrical diaryl sulfides has been developed by the C-S cross coupling of aryldithiocarbamates and aryldiazonium salts in the presence of CuI-2,2′-bipyridine and Zn. Aryldithiocarbamate compounds have been used here as thiol substitutes. The protocol shows wide substrate scope and good yields of the products.
- Dutta, Soumya,Saha, Amit
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p. 9360 - 9366
(2019/11/13)
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- Synthesis of Functionalized Diaryl Sulfides by Cobalt-Catalyzed Coupling between Arylzinc Pivalates and Diaryl Disulfides
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An efficient protocol for the cobalt-catalyzed preparation of diaryl sulfides from solid organozinc pivalates and commercially available diaryl disulfides is reported. This cross-coupling proceeds at room temperature and displays a good functional group tolerance, allowing the preparation of a diversity of symmetrical or asymmetrical diaryl sulfides in 60-95% yield.
- Dong, Zhi-Bing,Balkenhohl, Moritz,Tan, Eric,Knochel, Paul
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p. 7581 - 7584
(2018/11/27)
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- One-pot synthesis method for substituted diphenyl sulfide
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The invention relates to a one-pot synthesis method for substituted diphenyl sulfide. The process comprises the following steps: adding thiophenol or diphenyl disulfide and derivatives thereof into asolvent, dropwise adding sulfonyl chloride for a reaction so as to obtain a substituted benzene sulfuryl chloride solution, removing a part of the solvent at a normal pressure, adding Lewis acid, thendropwise adding substituted benzene for a Friedel-Crafts reaction, and carrying out distillation or recrystallization so as to obtain the substituted diphenyl sulfide. The method provided by the invention has the advantages of high safety, simple and convenient raw material recovery, greatly-reducedpurifying difficulty, easily-available raw materials, simple unit operation, low requirements on reaction equipment, mild reaction conditions, high yield and content and applicability to industrial production; and the content of the finally obtained substituted diphenyl sulfide product generally reaches 98% or more.
- -
-
Paragraph 0085; 0086; 0087
(2019/01/08)
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- Recyclable imidazolium ion-tagged nickel catalyst for microwave-assisted C-S cross-coupling in water using sulfonyl hydrazide as the sulfur source
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Herein, we report the facile and convenient synthesis of aryl sulfides through the sulfenylation of aryl halides with arylsulfonyl hydrazides, which is catalyzed by a simple and water-soluble Ni(ii) complex. The nickel complex based on the imidazolium ion-tagged salen architecture is synthesized and well characterized using various analytical techniques. The green solvent water is used as the solvent medium and moderate to good yields of aryl sulfides are obtained using 5 mol% of the catalyst under microwave irradiation. The incorporation of the ion-tag functionality helps in the recycling of the catalyst and successful reuse for up to five runs without appreciable change in its activity.
- Saini, Vaishali,Khungar, Bharti
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p. 12796 - 12801
(2018/08/04)
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- Synthesis of diaryl sulfides via nickel ferrite-catalysed C─S bond formation in green media
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NiFe2O4 magnetic nanoparticles (MNPs) were synthesized, characterized and applied as an air-stable, inexpensive and magnetically separable nanocatalyst for the synthesis of structurally diverse sulfides. Efficient methodologies were developed for the synthesis of unsymmetric diaryl sulfides via odourless and one-pot reactions of triphenyltin chloride/S8 or arylboronic acid/S8 as thiolating agents with aryl halides or nitroarenes as starting materials in the presence of base (K2CO3 or NaOH) and NiFe2O4 MNPs as a catalyst in water or poly (ethylene glycol) as solvent at 80–110?°C. Free from ligand and the unpleasant smell of thiols and with the use of magnetically reusable nanocatalyst, green solvents and commercially available and cheap sulfur source and starting materials, these methods are more eco-friendly and practical than available protocols for the synthesis of sulfides.
- Farzin, Shiva,Rahimi, Abdollah,Amiri, Kamran,Rostami, Abed,Rostami, Amin
-
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- Synthesis of o-Aryloxy Triarylsulfonium Salts via Aryne Insertion into Diaryl Sulfoxides
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The aryne insertion into "S-O" bond has been validated recently. This technology is elusively applied to the synthesis of thioethers. In contrast to the reported cases, the reaction described furnished o-aryloxy triarylsulfonium salts, in lieu of thioethe
- Li, Xiaojin,Sun, Yan,Huang, Xin,Zhang, Lei,Kong, Lichun,Peng, Bo
-
supporting information
p. 838 - 841
(2017/02/26)
-
- Mild synthesis of triarylsulfonium salts with arynes
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Reactions between arynes and alkyl sulfides have been extensively studied over the past few decades. These reactions commonly end with a dealkylation process and thus deliver thioethers as final products. In contrast, the transformation described furnishes valuable triarylsulfonium salts, in lieu of thioethers, from arynes and diarylsulfides. The reaction features mild conditions and a broad substrate scope. A suite of functional groups such as ketones, esters, nitriles, aryl ethers and aryl halides is tolerated, which can be issues faced by traditional synthetic methods. The practicality of the reaction and its extension to the synthesis of triphenyl selenonium salt are also exhibited herein.
- Zhang, Lei,Li, Xiaojin,Sun, Yan,Zhao, Weizhao,Luo, Fan,Huang, Xin,Lin, Lihui,Yang, Ying,Peng, Bo
-
supporting information
p. 7181 - 7189
(2017/09/07)
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- C-S cross-coupling of aryl halides with alkyl thiols catalyzed by in-situ generated nickel(II) N-heterocyclic carbene complexes
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The C-S cross-coupling of aryl halides with alkyl thiols catalyzed by in-situ generated Ni (II) N-heterocyclic carbene (NHC) complexes is investigated. Good to excellent yields can be obtained for a variety of aryl halides when using 5 mol% of the Ni (II)-NHC catalyst and 1.5 eq. of KOtBu. Both the electronic and steric effects of the NHC ligands on the catalytic performance of Ni (II)-NHC, as well as the electronic effects of aryl halides on coupling reactivity are examined. The mechanism for Ni (II)-NHC catalyzed coupling reactions is also discussed.
- Guo, Fang-Jie,Sun, Jing,Xu, Zhao-Qing,Kühn, Fritz E.,Zang, Shu-Liang,Zhou, Ming-Dong
-
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- Nickel(II) N-Heterocyclic Carbene Complexes: Versatile Catalysts for C–C, C–S and C–N Coupling Reactions
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A variety of NiII complexes with a wide range of electronic and steric properties, bearing picolylimidazolidene ligands (a–g) and Cp (Cp = η5-C5H5; 2a–f) or Cp* (Cp* = η5-C5Me5; 3a, c, g) groups, have been synthesised and characterised by using NMR spectroscopy and single-crystal X-ray crystallography. The complexes have been used as precatalysts for a wide range of catalytic transformations, which most likely involve a Ni0/NiII catalytic cycle. In particular, the new well-defined 2a, 2c, 3a and 3c complexes have demonstrated great efficiency and versatility towards Suzuki–Miyaura coupling reactions, hydroamination of activated olefins and C–S cross-coupling reactions of aryl halides and thiols under mild conditions.
- Junquera, Lourdes Benítez,Fernández, Francys E.,Puerta, M. Carmen,Valerga, Pedro
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supporting information
p. 2547 - 2556
(2017/05/29)
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- Visible-light-promoted synthesis of diaryl sulfides under air
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A convergent, organocatalytic visible-light-mediated process for the synthesis of diaryl sulfides has been developed. A broad range of aryl thiols reacted with various aryl diazonium salts in the presence of eosin Y under air atmosphere to afford the desired diaryl sulfides in high yields. This novel and environmentally friendly method provides an alternative route to established synthetic approaches.
- Hong, Boseok,Lee, Juyoung,Lee, Anna
-
supporting information
p. 2809 - 2812
(2017/06/27)
-
- An aryl thioether synthetic method of the compound
-
The invention discloses a synthetic method of an aryl sulfide type compound shown by a formula (3). In a reaction solvent, an aryl or alkenyl thiosulfate type derivative and a boric acid, boric acid grease or borate type derivative are used as reaction raw materials and react with each other to obtain a polysubstituted aryl sulfide type compound under the action of a metal copper catalyst. According to the synthetic method disclosed by the invention, reaction conditions are mild, raw materials are easily-available and low in price, the reaction operation is simple, the yield is relatively high, and a key skeleton structure is provided for the synthesis of many natural products and medicaments, so that the method can be widely applicable to industrial scale production. A formula is shown in the specification.
- -
-
Paragraph 0111; 0112; 0113; 0114
(2017/07/04)
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- A Highly Efficient Copper-Catalyzed Synthesis of Unsymmetrical Diaryl- and Aryl Alkyl Chalcogenides from Aryl Iodides and Diorganyl Disulfides and Diselenides
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An efficient and convenient protocol has been developed for the copper-catalyzed reaction of aryl iodides and diorganyl disulfides and diselenides. A variety of symmetrical and unsymmetrical diaryl- and aryl alkyl chalcogenides were synthesized with good functional group tolerance and chemoselectivity by using copper(I) iodide as a catalyst, 4′-(4-methoxyphenyl)-2,2′:6′,2′′-terpyridine as ligand, and KOH as base under an inert atmosphere.
- Movassagh, Barahman,Hosseinzadeh, Zhila
-
supporting information
p. 777 - 781
(2016/03/12)
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- Polystyrene resin-supported CuI-cryptand 22 complex: a highly efficient and reusable catalyst for the formation of aryl–sulfur bonds in aqueous media
-
The air and moisture stable polystyrene resin-supported copper(I) iodide-cryptand-22 complex (PS-C22-CuI) behaves as an efficient and robust heterogeneous catalyst in the cross-coupling reaction of aryl halides and thiols in aqueous media. Moreover, the heterogeneous catalyst can be easily recovered by filtration and reused for five cycles without significant loss in activity.
- Rezaei, Nasrin,Movassagh, Barahman
-
supporting information
p. 1625 - 1628
(2018/03/29)
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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
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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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- Copper and l-sodium ascorbate catalyzed hydroxylation and aryloxylation of aryl halides
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CuSO4·5H2O and NaAsc catalyzed hydroxylation and C-O/C-S cross-coupling reactions of aryl halides with phenols or 4-methylbenzenethiol were described. A wide range of substrates and test cases highlight the synthetic utility of the approach. A series of phenols, diaryl ethers, alkylaryl ethers, and diaryl thioethers were synthesized in high yield.
- Song, Guang-Lin,Zhang, Zhang,Da, Yu-Xia,Wang, Xi-Cun
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p. 8823 - 8829
(2015/10/20)
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- Magnetic nanoparticle-supported Pd(II)-cryptand 22 complex: An efficient and reusable heterogeneous precatalyst in the Suzuki-Miyaura coupling and the formation of aryl-sulfur bonds in honor and memory of late Prof. Mathias Mertes
-
In the present work, silica-coated magnetic nanoparticles [Fe3O4@SiO2@C22-Pd(II)] were prepared and characterized by transmission electron microscopy, Fourier transform infrared spectroscopy, vibrating sample magnetometer, energy dispersive X-ray analysis, X-ray photoelectron spectroscopy, elemental analysis, inductively coupled plasma, thermogravimetric and differential thermal analysis. This heterogeneous catalyst is utilized as an effective catalyst for the Suzuki-Miyaura coupling of arylboronic acids and aryl halides, and the cross-coupling reaction of aryl halides and thiols. The catalyst was easily separated by magnetic decantation and the recovered catalyst was reused for five cycles without any significant loss of the catalytic activity.
- Movassagh, Barahman,Takallou, Ahmad,Mobaraki, Akbar
-
-
- (1H-benzo[d][1,2,3]triazol-1-yl)methanol: An efficient bidentate ligand for copper catalyzed S-arylation of thiols
-
An operationally simple, palladium-free synthetic protocol for thio-arylation using 0.5 mol % CuI and 1 mol % (1H-benzo[d][1,2,3]triazol-1-yl)methanol as ligand is described. The ligand was found to be cheap, thermally stable, easy to synthesize, show simplicity in use and wide use in coupling reactions. Appropriately, the donor ability of the N=N bond of the benzotriazole ring and lone pair of electrons on the hydroxy group increases the bidentate ability of the ligand. Using this protocol, we have shown that a variety of aryl sulfides that can be synthesized in excellent yields from readily available aryl halide and thiols.
- Jhaa, Rajeev Ranjan,Choudharya, Deepak,Verma, Akhilesh K.
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p. 451 - 458
(2019/01/21)
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- The copper-nicotinamide complex: Sustainable applications in coupling and cycloaddition reactions
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The crystalline copper(ii)-nicotinamide complex, synthesized via simple mixing of copper chloride and nicotinamide solution at room temperature, catalyzes the C-S, C-N bond forming and cycloaddition reactions under a variety of sustainable reaction conditions.
- Baig, R.B. Nasir,Vaddula, Buchi Reddy,Nadagouda, Mallikarjuna N.,Varma, Rajender S.
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supporting information
p. 1243 - 1248
(2015/03/04)
-
- 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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- CO2-promoted oxidative cross-coupling reaction for C-S bond formation via masked strategy in an odourless way
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Cu-catalyzed direct oxidative cross-coupling between boronic acids and masked sulfides delivering thioethers was described, in which the SO3-, as a mask, has shown a distinctive effect on the oxidative cross-coupling condition. Disulfide could be suppressed efficiently via masked strategy under CO2 atmosphere. A broad scope of aromatics and scalable processes indicates its practicality, which could be further applied to drug late-stage modification and unsymmetrical dibenzothiophenes (DBTs) synthesis.
- Qiao, Zongjun,Ge, Nanyang,Jiang, Xuefeng
-
supporting information
p. 10295 - 10298
(2015/06/25)
-
- Nickel-catalyzed C-S bond formation: Synthesis of aryl sulfides from arylsulfonyl hydrazides and boronic acids
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A practical nickel-catalysed approach has been developed for the C-S bond formation through the cross-coupling of arylsulfonyl hydrazides and aryl boronic acids. The report employs arylsulfonyl hydrazide as an aryl thiol equivalent and offers a mild and eco-safe synthesis of unsymmetrical thioethers in good to excellent yields in air. The scope and versatility of the method has been successfully demonstrated with 22 examples.
- Singh, Rahul,Allam, Bharat Kumar,Singh, Neetu,Kumari, Kumkum,Singh, Satish Kumar,Singh, Krishna Nand
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supporting information
p. 1181 - 1186
(2015/04/22)
-
- Copper mediated formation of carbon-heteroatom bonds using organoboron reagents and ultrasound
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This report summarizes research efforts focused on copper acetate mediated reactions to form new carbon-heteroatom bonds using organoboron reagents under ultrasound irradiation. The method involves the application of ultrasound irradiation to the Chan-Evans-Lam reaction to achieve O-arylation of phenols, N-arylation of anilines and indoles, and S-arylation of thiols. Ultrasound irradiation was found to decrease reaction times from 72 hours to 4 hours while improving the product yields an average of 20%.1 Representative C-O, C-N, and C-S coupling reactions were successfully scaled-up from the milligram to gram levels while maintaining good product yields offering potential applications in industrial processes.
- Musolino, Bryan J.,Kabalka, George W.
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p. 271 - 297
(2015/03/04)
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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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- Carbon-sulfur bond formation catalyzed by [Pd(IPr*OMe) (cin)Cl] (cin = cinnamyl)
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The newly prepared complex [Pd(IPr*OMe)(cin)(Cl)] provides high catalytic activity for carbon-sulfur cross-coupling reactions. Nonactivated and deactivated aryl halides were successfully coupled with a large variety of aryl- and alkylthiols using this well-defined palladium N-heterocyclic carbene (NHC) complex.
- Bastug, Gulluzar,Nolan, Steven P.
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supporting information
p. 9303 - 9308
(2013/10/08)
-
- Organic synthesis via magnetic attraction: Benign and sustainable protocols using magnetic nanoferrites
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Magnetic nano-catalysts have been prepared using simple modification of iron ferrites. The nm size range of these particles facilitates the catalysis process, as an increased surface area is available for the reaction; the easy separation of the catalysts by an external magnet and their recovery and reuse are additional beneficial attributes. Glutathione bearing nano-ferrites have been used as organocatalysts for the Paal-Knorr reaction and homocoupling of boronic acids. Nanoferrites, post-synthetically modified by ligands, were used to immobilize nanometals (Cu, Pd, Ru, etc.) which enabled the development of efficient, sustainable and green procedures for azide-alkynes-cycloaddition (AAC) reactions, C-S coupling, O-allylation of phenol, Heck-type reactions and hydration of nitriles.
- Nasir Baig,Varma, Rajender S.
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p. 398 - 417
(2013/03/14)
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- Convenient MW-assisted synthesis of unsymmetrical sulfides using sulfonyl hydrazides as aryl thiol surrogate
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An efficient synthesis of unsymmetrical sulfides has been achieved via the cross-coupling reaction of aryl/het-aryl/benzyl halides with stable and easily workable sulfonyl hydrazides as thiol substitutes by means of [DBU][HOAc] and CuI under microwave irr
- Singh, Neetu,Singh, Rahul,Raghuvanshi, Dushyant S.,Singh, Krishna Nand
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supporting information
p. 5874 - 5877
(2013/12/04)
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- A highly active and magnetically retrievable nanoferrite-DOPA-copper catalyst for the coupling of thiophenols with aryl halides
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Diaryl sulfides were synthesized using a magnetically recoverable heterogeneous Cu catalyst via one-pot multi component reaction using MW irradiation; the use of isopropanol as a benign reaction medium, easy recovery of the catalyst using an external magnet, efficient recycling, and the high stability of the catalyst render the protocol economic and sustainable. This journal is The Royal Society of Chemistry 2012.
- Baig, R. B. Nasir,Varma, Rajender S.
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supporting information; experimental part
p. 2582 - 2584
(2012/03/26)
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- A general rhodium-catalyzed cross-coupling reaction of thiols with aryl iodides
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The general procedure for the rhodium-catalyzed cross-coupling of thiols with aryl iodides is described. The catalytic system consists of 5 mol % of [RhCl(cod)]2 and 10 mol % of PPh3 as a ligand. A variety of aryl iodides reacted with thiols, giving aryl thioethers in good to excellent yields. It is important to note that the deactivated aryl iodides such as 4-iodoanisole is worked smoothly to provide the corresponding aryl thioethers in excellent yields. Functional groups such as free-amines, chloro, are all tolerated under the employed reaction conditions.
- Lai, Chih-Shin,Kao, Hsin-Lun,Wang, Yan-Jhang,Lee, Chin-Fa
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supporting information; experimental part
p. 4365 - 4367
(2012/09/22)
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- Self-assembled NiO-ZrO2 nanocrystals with mesoscopic void space: An efficient and green catalyst for C-S cross-coupling reaction in water
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New NiO-ZrO2 nanocrystals (MNZ-1) with mesoscopic self-assembly have been synthesized by using a non-ionic surfactant as the structure directing agent (SDA) via evaporation induced self-assembly (EISA) method. Powder X-ray diffraction (PXRD), N
- Pal, Nabanita,Bhaumik, Asim
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experimental part
p. 9161 - 9169
(2012/08/28)
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- Cross-coupling reactions of aryl halides with amines, phenols, and thiols catalyzed by an N,N′-dioxide-copper(I) catalytic system
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The coupling reactions of various N, O, and S nucleophilic reagents with aryl halides have been successfully carried out under mild conditions by using a novel chiral N,N′-dioxide-copper(I) catalytic system as the catalyst. This versatile and efficient catalyst system has been demonstrated to facilitate the cross-coupling reactions of aryl halides with amines, phenols, and thiols to afford the corresponding desired products in good to excellent yields.
- Yang, Haitao,Xi, Chao,Miao, Zhiwei,Chen, Ruyu
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supporting information; experimental part
p. 3353 - 3360
(2011/08/03)
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- Cu-catalyzed carbon-heteroatom coupling reactions under mild conditions promoted by resin-bound organic ionic bases
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Resin-bound organic ionic bases (RBOIBs) were developed in which tetraalkyl-ammonium or phosphonium cations are covalently attached to solid resins. The application tests showed that the performance of the tetraalkyl-ammonium-type RBOIBs is slightly better than that of the corresponding Cs salts in Cu-catalyzed C-N cross-couplings, while the tetraalkylphosphonium-type RBOIBs are significantly better than all the inorganic bases. With these newly developed RBOIBs, room-temperature Cu-catalyzed C-Ncoupling with various nonactivated aryl iodides and even aryl bromides can be readily accomplished. Moreover, RBOIBs can be easily recycled and reused for a number of times without much drop of activity. The good performances of RBOIBs are proposed to arise from the relatively weak binding forces between the cationic polymer backbone and basic anions, as opposed to the strong metal-anion interactions in the inorganic bases. Further applications of RBOIBs in Ni-catalyzed Suzuki-type couplings at room temperature, Cu-catalyzed C-N couplings at -30 °C, a Pd-catalyzed Heck reaction at 60 °C, and Cu-catalyzed C-S couplings at room temperature demonstrate that RBOIBs are generally applicable bases with improved performance for many other types of organic transformations.
- Huang, Yao-Bing,Yang, Chu-Ting,Yi, Jun,Deng, Xiao-Jian,Fu, Yao,Liu, Lei
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experimental part
p. 800 - 810
(2011/04/22)
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- A highly efficient, ligand-free, and recyclable Cu2S-catalyzed coupling of aryl iodides with diaryl disulfides
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A highly efficient and ligand-free copper(I) sulfide catalyzed cross-coupling reaction of aryl iodides with diaryl disulfides was developed. With only 1 mol-% of Cu2S as the catalyst, iron powder as the reductant, and K2CO3 as the base, aryl iodides reacted with disulfides in DMSO at 90-110 °C for 18-24 h under an atmosphere of argon to give the corresponding aryl sulfides in good to excellent yields. In addition, the catalyst is recyclable and reusable with some loss of activity.
- Wang, Huifeng,Jiang, Linlin,Chen, Tao,Li, Yarning
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experimental part
p. 2324 - 2329
(2010/07/10)
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- C-S bond formation catalyzed by N-heterocylic carbene palladium phosphine complexes
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N-Heterocyclic carbenes (NHCs) are known to be useful ligands for palladium-complex catalysis. It was found that [(NHC)Pd(PPh3)Cl2] is an effective pre-catalyst in Pd-catalyzed C-S cross coupling reactions to produce the functionalized sulfides in excellent yields. The turn over frequency (TOF) for the coupling of p-CH3C6H4Br with p-CH3C6H4SH reaches to 6.25 (mol of product) (mole of catalyst)-1 h-1.
- Fu, Ching-Feng,Liu, Yi-Hung,Peng, Shei-Ming,Liu, Shiuh-Tzung
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experimental part
p. 2119 - 2122
(2010/04/26)
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- Well-defined allylnickel chloride/N-heterocyclic carbene [(NHC)Ni (allyl)Cl] complexes as highly active precatalysts for C-N and C-S cross-coupling reactions
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The room temperature Buchwald-Hartwig amination of heteroaromatic chlorides has been achieved using the sterically bulky allylnickel chloride/ N-heterocyclic carbene [(IPr)Ni (allyl)Cl]complex as a well-defined precatalyst. Arylation of aromatic thiols, affording high yields of products under low catalyst loadings, has also been promoted with the same complex.
- Iglesias, Maria Jose,Prieto, Auxiliadora,Nicasioa, M. Carmen
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supporting information; experimental part
p. 1949 - 1954
(2010/10/21)
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- A reusable FeCl3·6H2O/cationic 2,2′-bipyridyl catalytic system for the coupling of aryl iodides with thiols in water under aerobic conditions
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In this study, an FeCl3·6H2O/cationic 2,2′-bipyridyl system was employed as a catalyst in the coupling of aryl iodides with thiols to form an aryl-sulfur bond in refluxed water under aerobic conditions. The residual aqueous solution after extraction could be reused for several cycles without a significant decrease in activity.
- Wu, Wei-Yi,Wang, Jui-Chan,Tsai, Fu-Yu
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experimental part
p. 326 - 329
(2010/04/22)
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- Copper-catalyzed Ullmann coupling under ligand- and additive-free conditions. Part 2: S-Arylation of thiols with aryl iodides
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S-Arylation of a wide variety of substituted aryl and aliphatic thiols with aryl halides catalyzed by copper iodide under mild ligand- and additive-free conditions (nBu4NBr, PhMe, NaOH, reflux, 22 h) is accomplished in good to excellent product yields (up to 96%).
- Buranaprasertsuk, Pongchart,Chang, Joyce Wei Wei,Chavasiri, Warinthorn,Chan, Philip Wai Hong
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p. 2023 - 2025
(2008/09/19)
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- A general and efficient CuI/BtH catalyzed coupling of aryl halides with thiols
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We report an exceptionally mild, general and efficient copper catalyzed cross coupling reaction of aryl bromides and thiols using 0.5 mol % CuI and 1 mol % benzotriazole. Experimental simplicity, generality, functional group tolerance and low cost of the catalyst are advantages of the protocol.
- Verma, Akhilesh Kumar,Singh, Jaspal,Chaudhary, Ritu
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p. 7199 - 7202
(2008/03/11)
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- "β-cis-SAr effect" on decarbonylation from α,β-unsaturated acyl and aroyl complexes
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Lone pair of heteroatom located at the β-cis position in α,β-unsaturated acyl and aroyl group 10 metal complexes dramatically facilitated the stoichiometric and catalytic decarbonylation reactions. The Royal Society of Chemistry 2006.
- Kato, Tomohiro,Kuniyasu, Hitoshi,Kajiura, Takamichi,Minami, Yasunori,Ohtaka, Atsushi,Kinomoto, Masanori,Terao, Jun,Kurosawa, Hideo,Kambe, Nobuaki
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p. 868 - 870
(2008/02/08)
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- Cobalt-catalyzed aryl-sulfur bond formation
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A new cobalt-catalyzed coupling of aryl halides with thiophenols and alkanethiols is reported. A variety of aryl sulfides can be prepared in excellent yields under mild reaction conditions using 1-2 mol % of Col2(dppe) and Zn. This new cobalt-catalyzed coupling represents an interesting addition to previously known methods to synthesize thioethers.
- Wong, Ying-Chieh,Jayanth, Thiruvellore Thatai,Cheng, Chien-Hong
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p. 5613 - 5616
(2007/10/03)
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