- A general and inexpensive protocol for the Cu-catalyzed C-S cross-coupling reaction between aryl halides and thiols
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A cost effective and easily available CuI/DABCO catalytic system has been developed for C-S cross-coupling reaction. This method is extremely useful for the thioetherification of aryl and heteroaryl halides providing excellent yields and good chemoselectivity.
- Thomas, Anns Maria,Asha, Sujatha,Sindhu,Anilkumar, Gopinathan
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- Generation of Thiyl Radicals from Air-Stable, Odorless Thiophenol Surrogates: Application to Visible-Light-Promoted C-S Cross-Coupling
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The synthetic versatility of thiophenols is offset by their airsensitivity and foul odor. It is demonstrated that S-aryl isothiouronium salts can be used as precursors to thiyl radicals, extending the practical benefits of these air-stable, odorless salts from ionic to single electron manifolds. The isothiouronium salts are accessed via Ni-catalyzed crosscoupling of (hetero)aryl iodides and thiourea and are isolated as freeflowing solids following anion exchange. Judicious choice of a redox-innocent counteranion enables use of these convenient thiophenol surrogates in radical processes, as is exemplified by the synthesis of nonsymmetrical diaryl thioethers via light-promoted S-arylation.
- Ball, Liam T.,Maggi, Lorenzo,Park, Mahri,Shepherd, William,Swan, Charlie,Taylor, Sophie
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- Forging C?S(Se) Bonds by Nickel-catalyzed Decarbonylation of Carboxylic Acid and Cleavage of Aryl Dichalcogenides
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A nickel-catalyzed decarbonylation of carboxylic acids cross-coupling protocol has been developed for the straightforward C?S(Se) bond formation. This reaction is promoted by a commercially-available, user-friendly, inexpensive, air and moisture-stable nickel precatalyst. Various carboxylic acids and a wide range of aryl dichalcogenide substrates were tolerated in this process which afforded products in good to excellent yields. In addition, the present reaction can be conducted on gram scale in good yield.
- Zhou, Jing-Ya,Zhu, Yong-Ming
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p. 2452 - 2461
(2021/06/28)
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- Exploration of the mechanism and scope of the CuI/DABCO catalysed C–S coupling reaction
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A cost effective and easily available CuI/DABCO catalytic system has been developed for the C–S cross-coupling reaction. This method is extremely useful for the thioetherification of aryl and heteroaryl halides, providing excellent yields and good chemoselectivity. We have also explored the mechanism of the reaction using DFT studies.
- Thomas, Anns Maria,Sherin,Asha, Sujatha,Manojkumar,Anilkumar, Gopinathan
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supporting information
(2019/12/26)
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- HETEROCYCLIC CARBOXYLIC ACID AMIDE LIGAND AND APPLICATIONS THEREOF IN COPPER CATALYZED COUPLING REACTION OF ARYL HALOGENO SUBSTITUTE
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Provided are a heterocyclic carboxylic acid amide ligand and applications thereof in a copper catalyzed coupling reaction. Specifically, provided are uses of a compound represented by formula (I), definitions of radical groups being described in the specifications. The compound represented by formula (I) can be used as the ligand in the copper catalyzed coupling reaction of the aryl halogeno substitute, and is used or catalyzing the coupling reaction for forming the aryl halogeno substitute having C—N, C—O, C—S and other bonds.
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Paragraph 0287-0288
(2019/05/15)
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- Electrochemically Promoted Nickel-Catalyzed Carbon-Sulfur Bond Formation
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This work describes a nickel-catalyzed Ullmann-type thiolation of aryl iodidesunder mild electrochemical conditions. The simple undivided cell with graphene/nickel foam electrode setups offers excellent substrate tolerance, affording aryl and alkyl sulfides in good chemical yields. Furthermore, the mechanism for this electrochemical cross-coupling reaction has been investigated by cyclic voltammetry.
- Wang, Yang,Deng, Lingling,Wang, Xiaochen,Wu, Zhengguang,Wang, Yi,Pan, Yi
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p. 1630 - 1634
(2019/03/08)
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- An efficient protocol for the synthesis of thioethers via iron-catalyzed cross-coupling reaction and its mechanistic investigation
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One of the most straightforward methods for the synthesis of diaryl sulfides is the transition metal catalyzed C–S coupling reaction. Herein we report a study on the iron-catalyzed protocol for cross-coupling reaction of aryl halides with thiols. Structurally diverse diaryl sulfides were prepared efficiently by using a catalyst system involving cheap and environment-friendly FeCl3 and non-toxic universal ligand L-proline. The reaction mechanism for the iron-catalyzed C–S coupling reaction was investigated by means of density functional theory (DFT) methods on a model system. The calculations were performed using hybrid PBE1PBE functional in conjugation with the LANL-2DZ basis set. The key step involved in the mechanism is the formation of a reactant complex in which both reactants are electrostatically bound to Fe(III) proline complex catalyst. The elimination of HI occurs with a much lower TS energy (20.0 kcal/mol) than the uncatalyzed reaction (44.7 kcal/mol).
- Sindhu,Abi,Mathai, George,Anilkumar, Gopinathan
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p. 270 - 276
(2018/11/26)
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- PHOTOCATALYST-FREE, LIGHT-INDUCED CARBON-SULFUR CROSS-COUPLING METHODS
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In one aspect, the invention provides a method of promoting a carbon-sulfur bond forming reaction. In certain embodiments, the reaction comprises cross-coupling of a(n) (hetero)aryl halide with a thiol to form the carbon-sulfur bond, wherein the method is promoted by light irradiation in the absence of a photocatalyst. In other embodiments, the cross-coupling reaction can be promoted through visible light irradiation, including sunlight.
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Paragraph 0097; 0116; 0117
(2019/01/10)
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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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- Cu(ii)-catalyzed sulfide construction: both aryl groups utilization of intermolecular and intramolecular diaryliodonium salt
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A sulfur-iodine exchange protocol of diaryliodonium salts with inorganic sulfur salt was developed. Both aryl groups in the diaryliodonium salt were fully exerted in this transformation. Five- to eight-membered sulfur-containing heterocycles were achieved. Note that [1]benzothieno-[3,2-b][1]benzothiophene (BTBT) (an organic field-effect transistor (OFET) material) and Zaltoprofen were efficiently established through this method.
- Wang, Ming,Wei, Jianpeng,Fan, Qiaoling,Jiang, Xuefeng
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supporting information
p. 2918 - 2921
(2017/03/15)
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- Visible-light-promoted C-S cross-coupling via intermolecular charge transfer
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Disclosed is a mild, scalable, visible-lightpromoted cross-coupling reaction between thiols and aryl halides for the construction of C-S bonds in the absence of both transition metal and photoredox catalysts. The scope of aryl halides and thiol partners includes over 60 examples and therefore provides an entry point into various aryl thioether building blocks of pharmaceutical interest. Furthermore, to demonstrate its utility, this C-S coupling protocol was applied in drug synthesis and latestage modifications of active pharmaceutical ingredients. UV-vis spectroscopy and time-dependent density functional theory calculations suggest that visible-lightpromoted intermolecular charge transfer within the thiolate-aryl halide electron donor-acceptor complex permits the reactivity in the absence of catalyst.
- Liu, Bin,Lim, Chern-Hooi,Miyake, Garret M.
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supporting information
p. 13616 - 13619
(2017/11/06)
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- Diaryl thioether compound, and synthetic method and application thereof
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The invention discloses a diaryl thioether compound, and a synthetic method and an application thereof. Various diaryl thioether compounds can be obtained through a reaction of a reaction raw material high iodine salt in dimethyl sulfoxide at 60-100DEG C under the action of an odorless sulfuration reagent, an alkali, a metal catalyst and a ligand for 3-12h. Sulfur is introduced in the later stage, so poisoning of sulfur to the metal catalyst and incompatibility of an oxidant in the early stage reaction are avoided; the above inorganic sulfur source is nontoxic and odorless; and two aryl groups in the high iodine salt are fully used, so the atom economy of the method is fully shown. The diaryl thioether compound prepared through the method can be further used to synthesize a photoelectric material BTBT and an anti-inflammatory drug zaltoprofen.
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Paragraph 0065-0069
(2018/02/04)
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- A novel and efficient zinc-catalyzed thioetherification of aryl halides
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The first zinc-catalysed protocol for the C-S cross-coupling reaction is reported. Zinc catalysis has an undeniable advantage over other catalytic systems as it is non-toxic, and the catalysts are easily available and cheap, with environmentally benign properties. This novel, efficient, palladium- and triphenylphosphine-free protocol yielded a variety of aryl and alkyl sulfides in moderate to excellent yields. This journal is
- Thankachan, Amrutha P.,Sindhu,Krishnan, K. Keerthi,Anilkumar, Gopinathan
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p. 32675 - 32678
(2015/04/27)
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- An efficient iron-catalyzed S-arylation of aryl and alkylthiols with aryl halides in the presence of water under aerobic conditions
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Abstract In this study, an environmentally benign FeCl3·6H2O/l-proline catalytic system in the presence of TBAB was employed as a catalyst for the coupling reactions of aryl halides with aryl and alkyl thiols in water under aerobic conditions. The versatility, low cost, and environmental friendliness, in combination with high yields, makes the procedure noteworthy. This protocol offers a simple and efficient thioetherification method for aryl halides.
- Sindhu,Thankachan, Amrutha P.,Thomas, Anns Maria,Anilkumar, Gopinathan
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supporting information
p. 4923 - 4926
(2015/07/28)
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- Ionic liquid as base and phase transfer agent: A green protocol for the synthesis of diaryl sulphides in water
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A basic ionic liquid, 1-methyl-3-butylimidazolium hydroxide, [BMIm]OH, acts as a base and phase transfer agent in the copper-catalysed ligand free S-arylation in water. A variety of iodo and bromoaryl compounds undergo coupling with aryl and heteroaryl thiols in presence of this ionic liquid in water to provide the corresponding diaryl/aryl-heteroaryl sulfides. The use of benign [BMIm]OH and water as reaction medium makes this procedure greener and cost effective.
- Kundu, Debasish,Ranu, Brindaban C.
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p. 1761 - 1765
(2014/01/17)
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- Microwave-assisted reaction of aryl diazonium fluoroborate and diaryl dichalcogenides in dimethyl carbonate: A general procedure for the synthesis of unsymmetrical diaryl chalcogenides
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A convenient, general and efficient procedure for the synthesis of unsymmetrical diaryl chalcogenides has been developed by the reaction of aryl diazonium fluoroborates and diaryl dichalcogenides in the presence of zinc dust in dimethyl carbonate under microwave irradiation. The reactions of a wide range of substituted aryl diazonium fluoroborates and diaryl dichalcogenides have been addressed. The zinc dust is required for the cleavage of diaryl dichalcogenides. The products are obtained in high purity after fast column chromatography of the crude residue after evaporation of dimethyl carbonate. The Royal Society of Chemistry 2012.
- Kundu, Debasish,Ahammed, Sabir,Ranu, Brindaban C.
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experimental part
p. 2024 - 2030
(2012/07/17)
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- One-pot synthesis of symmetrical and unsymmetrical aryl sulfides by Pd-catalyzed couplings of aryl halides and thioacetates
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Aryl sulfides were obtained from the coupling reaction of S-aryl (or S-alkyl) thioacetates and aryl bromides in the presence of palladium catalyst. This reaction method enables the one-pot synthesis of symmetrical and unsymmetrical diaryl sulfides by employing potassium thioacetate with aryl iodides and aryl bromides.
- Park, Namjin,Park, Kyungho,Jang, Mihee,Lee, Sunwoo
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experimental part
p. 4371 - 4378
(2011/07/06)
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- Oxidoreductive coupling of thiols with aryl halides catalyzed by copper on iron
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Synthesis and utilization of a simple copper on iron catalyst in the coupling of aryl halides with thiols through disulfide intermediate is reported. The iron support of copper catalyst ensures reductive media for the coupling, allows easy removal of the metals by outer magnetic field and enables the recycling of the catalyst.
- Kovacs, Szabolcs,Novak, Zoltan
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experimental part
p. 711 - 716
(2011/03/22)
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- The synthesis and SAR of novel diarylsulfone 11β-HSD1 inhibitors
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In this communication, human 11β-hydroxysteroid dehydrogenase type 1 (11β-HSD1) inhibitory activities of a novel series of diarylsulfones are described. Optimization of this series resulted in several highly potent 11β-HSD1 inhibitors with excellent pharmacokinetic (PK) properties. Compound (S)-25 showed excellent efficacy in a non-human primate ex vivo pharmacodynamic model.
- Yan, Xuelei,Wang, Zhulun,Sudom, Athena,Cardozo, Mario,Degraffenreid, Michael,Di, Yongmei,Fan, Pingchen,He, Xiao,Jaen, Juan C.,Labelle, Marc,Liu, Jinsong,Ma, Ji,McMinn, Dustin,Miao, Shichang,Sun, Daqing,Tang, Liang,Tu, Hua,Ursu, Stefania,Walker, Nigel,Ye, Qiuping,Powers, Jay P.
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scheme or table
p. 7071 - 7075
(2011/01/03)
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- Rhodium-catalyzed substitution reaction of aryl fluorides with disulfides: P-orientation in the polyarylthiolation of polyfluorobenzenes
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In the presence of a catalytic amount of RhH(PPh3)4 and 1,2-bis(diphenylphosphino)benzene, an aromatic fluoride, an organic disulfide (0.5 equiv), and triphenylphosphine (0.5 equiv) reacted in refluxing chlorobenzene to give an aryl sulfide in high yield. Since triphenylphosphine trapped fluoride atoms forming phosphine difluoride, both organothio groups of the disulfide reacted effectively, and the fluoride substituent reacted more readily than the chloride and bromide. The reaction of hexafluorobenzene and a diaryl disulfide gave 1,4-diarylthio-2,3,5,6-tetrafluorobenzene, 1,2,4,5-tetraarylthio-3,6-difluorobenzene, and hexaarylthiobenzene in a stepwise manner; pentafluorobenzene gave 1-arylthio-2,3,5,6-tetrafluorobenzene; 1,2,3,4-tetrafluorobenzene gave 1,2-diarylthio-3,6-difluorobenzene; and 1,2,4,5-tetrafluorobenzene gave 1,4-diarylthio-2-5-difluorobenzene. The polyarylthiolation reaction of polyfluorobenzenes exhibited a strong tendency to form 1,4-difluorobenzenes. Copyright
- Arisawa, Mieko,Suzuki, Takaaki,Ishikawa, Tomofumi,Yamaguchi, Masahiko
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supporting information; scheme or table
p. 12214 - 12215
(2009/02/04)
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- SUBSTITUTED 4-ARYLOXY AND 4-ARYLSULFANYL-PHENYL-2-AMINOTHIAZOLES AS INHIBITORS OF CELL PROLIFERATION
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The invention discloses compounds which are substituted 4-aryloxy and 4-arylsulfanyl-phenyl-2-aminothiazoles with anti-cancer activity. The invention futher discloses methods of preparing compounds of the invention. The invention also discloses methods of inhibiting cell proliferation and tumor growth in a subject by administering compounds of the invention to the subject.
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Page/Page column 30-33
(2008/06/13)
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- Nickel(O)-catalyzed Synthesis of Diaryl Sulfides from Aryl Halides and Aromatic Thiols
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Facile and selective syntheses of various diaryl sulfides from aryl halides and aromatic thiols by the aid of an in situ generated nickel(O) catalyst are reported.The nickel(O) induces a C-S cleavege, as well.
- Takagi, Kentaro
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p. 2221 - 2224
(2007/10/02)
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