- Chan-Lam-Type C-S Coupling Reaction by Sodium Aryl Sulfinates and Organoboron Compounds
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A Chan-Lam-Type C-S coupling reaction using sodium aryl sulfinates has been developed to provide diaryl thioethers in up to 92% yields in the presence of a copper catalyst and potassium sulfite. Both electron-rich and electron-poor sodium aryl sulfinates and diverse organoboron compounds were tolerated for the synthesis of aryl and heteroaryl thioethers and dithioethers. The mechanistic study suggested that potassium sulfite was involved in the deoxygenation of sulfinate through a radical process.
- Lam, Long Yin,Ma, Cong
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supporting information
p. 6164 - 6168
(2021/08/16)
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- Safe, Scalable, Inexpensive, and Mild Nickel-Catalyzed Migita-Like C?S Cross-Couplings in Recyclable Water
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A new approach to C?S couplings is reported that relies on nickel catalysis under mild conditions, enabled by micellar catalysis in recyclable water as the reaction medium. The protocol tolerates a wide range of heteroaromatic halides and thiols, including alkyl and heteroaryl thiols, leading to a variety of thioethers in good isolated yields. The method is scalable, results in low residual metal in the products, and is applicable to syntheses of targets in the pharmaceutical area. The procedure also features an associated low E Factor, suggesting a far more attractive entry than is otherwise currently available, especially those based on unsustainable loadings of Pd catalysts.
- Yu, Tzu-Yu,Pang, Haobo,Cao, Yilin,Gallou, Fabrice,Lipshutz, Bruce H.
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supporting information
p. 3708 - 3713
(2020/12/17)
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- A Robust Pd-Catalyzed C-S Cross-Coupling Process Enabled by Ball-Milling
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An operationally simple mechanochemical C-S coupling of aryl halides with thiols has been developed. The reaction process operates under benchtop conditions without the requirement for a (dry) solvent, an inert atmosphere, or catalyst preactivation. The reaction is finished within 3 h. The reaction is demonstrated across a broad range of substrates; the inclusion of zinc metal has been found to be critical in some instances, especially for coupling of alkyl thiols.
- Browne, Duncan L.,Jones, Andrew C.,Nicholson, William I.,Smallman, Harry R.
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supporting information
p. 7433 - 7438
(2020/10/09)
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- Syntheses of Thioethers and Selenide Ethers from Anilines
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In this study, a general procedure was proposed for synthesizing thioethers and selenide ethers from anilines under solvent-free and transition-metal-free conditions. Thioethers were formed when anilines reacted with thiols under blue light-emitting-diode (LED) irradiation at room temperature without a photocatalyst. When reactions were performed using anilines and diselenides, the corresponding selenide ethers were obtained with satisfactory to excellent yields. The reaction was performed under photocatalyst-free and solvent-free conditions without blue LEDs. The advantages of this system include convenient operations, mild reaction conditions, satisfactory functional group tolerance, and late-stage selenylation of drug molecules.
- Shieh, Yi-Chen,Du, Kai,Basha, R. Sidick,Xue, Yung-Jing,Shih, Bo-Hao,Li, Liang,Lee, Chin-Fa
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p. 6223 - 6231
(2019/05/24)
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- Copper-Catalyzed Electrophilic Thiolation of Organozinc Halides by Using N-Thiophthalimides Leading to Polyfunctional Thioethers
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(Hetero)aryl, benzylic, and alkyl zinc halides were thiolated with N-thiophthalimides at 25 °C within 1 h in the presence of 5–10 % Cu(OAc)2?H2O to furnish the corresponding polyfunctionalized thioethers in good yields. This electrop
- Gra?l, Simon,Hamze, Clémence,Koller, Thadd?us J.,Knochel, Paul
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p. 3752 - 3755
(2019/02/13)
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- Iodine(III) Enabled Dehydrogenative Aryl C?S Coupling by in situ Generated Sulfenium Ion
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Due to the normal polarity preferences, arenes form stable complexes with thiols through S?H???π interaction and direct dehydrogenative aryl C?S coupling is usually restricted. We report here an umpolung based one pot and direct C?S coupling approach unde
- Choudhuri, Khokan,Maiti, Saikat,Mal, Prasenjit
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p. 1092 - 1101
(2019/01/30)
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- CuI promoted sulfenylation of organozinc reagents with arylsulfonyl chlorides
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A CuI promoted sulfenylation of organozinc reagents with arylsulfonyl chlorides/PPh3 has been explored. This reaction proceeded smoothly through an alkyl/aryl radical (generated from organometallics) under mild conditions and produced the desired sulfide products in excellent yields.
- Fu, Ying,Su, Yuhu,Xu, Qin-Shan,Du, Zhengyin,Hu, Yulai,Wang, Ke-Hu,Huang, Danfeng
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p. 6018 - 6022
(2017/02/05)
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- Copper-catalyzed sulfenylation of boronic acids with sulfonyl hydrazides
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An unprecedented sulfenylation reaction of carbon-boron bonds has been developed using sulfonyl hydrazides as sulfenyl sources. A range of sulfonyl hydrazides underwent tetrakis(acetonitrile)copper(I) tetrafluoroborate [Cu(CH3CN)4BF4]/2,2′-bipyridine-catalyzed sulfenylation with boronic acids under air to give structurally diverse thioethers in moderate to good yields. Preliminary mechanistic studies show that sulfonyl hydrazides are subjected to decomposition into thiosulfonates and disulfides followed by formation of carbon-sulfur bonds with boronic acids.
- Wang, Ting-Ting,Yang, Fu-Lai,Tian, Shi-Kai
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supporting information
p. 928 - 932
(2015/03/30)
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- Synthesis of Aryl Sulfides: Metal-Free C-H Sulfenylation of Electron-Rich Arenes
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A simple, efficient, and practical metal-free C-H sulfenylation of substituted electron-rich arenes has been developed. This method is highly regioselective, and the corresponding aryl sulfides were obtained in moderate to excellent yields from stable and
- Hostier, Thomas,Ferey, Vincent,Ricci, Gino,Gomez Pardo, Domingo,Cossy, Janine
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supporting information
p. 3898 - 3901
(2015/08/18)
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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)
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- An efficient protocol for the carbon-sulfur cross-coupling of sulfenyl chlorides with arylboronic acids using a palladium catalyst
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An efficient protocol for carbon-sulfur bond formation is developed, which involves the cross-coupling of sulfenyl chlorides and arylboronic acids catalyzed by a novel palladium-Schiff base complex. Good to high product yields, short reaction times, and mild reaction conditions are important features of this new method. Georg Thieme Verlag Stuttgart · New York.
- Gogoi, Prasanta,Kalita, Mukul,Barman, Pranjit
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p. 866 - 870
(2014/04/03)
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- Palladium catalyzed aryl(alkyl)thiolation of unactivated arenes
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A general palladium-catalyzed aryl(alkyl)thiolation of various substituted unactivated arenes is accomplished for the synthesis of diverse unsymmetrical diaryl(alkyl) sulfides in good yield employing electrophilic sulfur reagent 6 derived from succinimide. The developed strategy was coupled with intramolecular arylation of a C-H bond to afford dibenzothiphene derivatives, an important moiety in material science as organic semiconductors.
- Saravanan, Perumal,Anbarasan, Pazhamalai
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p. 848 - 851
(2014/03/21)
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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)
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- Transition-metal-free synthesis of unsymmetrical diaryl chalcogenides from arenes and diaryl dichalcogenides
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A transition-metal-free synthetic method has been developed for the synthesis of unsymmetrical diaryl chalcogenides (S, Se, and Te) from diaryl dichalcogenides and arenes under oxidative conditions by using potassium persulfate at room temperature. Variously substituted arenes such as anisole, thioanisole, diphenyl ether, phenol, naphthol, di- and trimethoxy benzenes, xylene, mesitylene, N,N-dimethylaniline, bromine-substituted arenes, naphthalene, and diaryl dichalcogenides underwent carbon-chalcogen bond-forming reaction to give unsymmetrical diaryl chalcogenides in trifluoroacetic acid. To understand the mechanistic part of the reaction, a detailed in situ characterization of the intermediates has been carried out by 77Se NMR spectroscopy by using diphenyl diselenide as the substrate. 77Se NMR study suggests that electrophilic species ArE+ is generated by the reaction of diaryl dichalcogenide with persulfate in trifluoroacetic acid. The electrophilic attack of arylchalcogenium ion on the arene may be responsible for the formation of the aryl-chalcogen bond.
- Prasad, Ch Durga,Balkrishna, Shah Jaimin,Kumar, Amit,Bhakuni, Bhagat Singh,Shrimali, Kaustubh,Biswas, Soumava,Kumar, Sangit
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p. 1434 - 1443
(2013/03/29)
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- 8-hydroxyquinolin-N-oxide-promoted copper-catalyzed C-S cross-coupling of thiols with aryl iodides
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8-Hydroxyquinolin-N-oxide was identified as a superior ligand for CuI-catalyzed C-S coupling reactions of aryl iodides with thiols to afford the corresponding thioethers in excellent yield. The method shows excellent chemoselectivity and high functional-group tolerance in both coupling partners. Copyright
- Su, Kun,Qiu, Yatao,Yao, Yiwu,Zhang, Dayong,Jiang, Sheng
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supporting information
p. 2853 - 2857
(2013/02/21)
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- Simple and efficient copper-catalyzed S-arylation of diaryl disulfides with triarylbismuthanes under aerobic conditions
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Novel and simple copper-catalyzed C(aryl)-S bond formation of diaryl disulfides with bismuth reagents is described. Reactions of diaryl disulfides with triarylbismuthanes in the presence of CuOAc (10 mol %) and 1,10-phenanthroline (10 mol %) under aerobic conditions led to the formation of unsymmetrical diaryl sulfides in satisfactory yields. The reaction is atom-economic and all three aryl groups of the triarylbismuthanes and both sulfanyl groups of the diaryl disulfides could be transferred to the coupling products.
- Yasuike, Shuji,Nishioka, Motokazu,Kakusawa, Naoki,Kurita, Jyoji
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experimental part
p. 6403 - 6406
(2011/12/22)
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- FeF3/i2-catalyzed synthesis of 4-chalcogen- substituted arylamines by direct thiolation of an arene C-H bond
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An efficient regioselective synthesis of 4-chalcogen-substituted-arylamines by FeF3-catalyzed sulfenylation and selenation of arylamines has been developed. In the presence of FeF3and I2, a variety of arylamines underwent the reaction with disulfides or diselenides to afford the corresponding 4-sulfenyl-or 4-selenenyl-arylamines in moderate to good yields. Georg Thieme Verlag Stuttgart.
- Fang, Xiao-Li,Tang, Ri-Yuan,Zhang, Xing-Guo,Li, Jin-Heng
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experimental part
p. 1099 - 1105
(2011/05/14)
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- Novel C-H functionalization of arenes: Palladium-catalyzed synthesis of diaryl sulfides
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A novel protocol for the direct arylthiolation of electron-rich arenes is described. Applying arylsulfonyl cyanides in the presence of catalytic amounts of Pd allows for a straightforward synthesis of diaryl sulfides.
- Anbarasan, Pazhamalai,Neumann, Helfried,Beller, Matthias
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supporting information; experimental part
p. 3233 - 3235
(2011/05/05)
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- An efficient copper-catalyzed cross-coupling reaction of thiols with aryl iodides
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Commercially available Cu2O powder is a very reactive catalyst for the coupling of thiols to aryl iodides. A variety of functional groups including esters, unprotected amines, alcohols, and heterocycles tolerate the reaction conditions. Moreover, di-ortho-substituted aryl iodides with sterically demanding substrates were also coupled to give the desired aryl thioethers in good to excellent yields. Copyright
- Kao, Hsin-Lun,Chen, Chin-Keng,Wang, Yu-Jen,Lee, Chin-Fa
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experimental part
p. 1776 - 1781
(2011/05/03)
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- Carbon-sulfur bond formation of challenging substrates at low temperature by using Pd-PEPPSI-IPent
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Aryl thiols made cool and quick: The coupling of alkyl, aryl, and silyl thiols to hindered, deactivated aryl bromides and chlorides has been achieved under the most mild temperatures yet reported (i.e., room temperature to 40°C). The bulk afforded by the di-2,6-(3-propylphenyl)imidazolium-derived Pd-PEPPSI-IPent catalyst is believed to actively promote the critical reductive elimination step of the catalytic cycle, thereby eliminating the formation of poisonous off-cycle dimeric resting states that have plagued Pd-catalyzed sulfination reactions.
- Sayah, Mahmoud,Organ, Michael G.
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supporting information; experimental part
p. 11719 - 11722
(2011/11/29)
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- Facile preparation of aryl sulfides catalyzed by PEG400 and nickel without solvent
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A variety of aryl sulfides were synthesized by aryl bromides with thiols, with PEG400 and nickel as catalysts under basic conditions in the absence of solvents. This article reported an easy and convenient method for formation of aryl-sulfur bonds. Copyright Taylor & Francis Group, LLC.
- Cao, Yu-Qing,Zhang, Zhan,Guo, Yan-Xin,Wu, Guo-Qiang
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p. 1325 - 1332
(2008/09/19)
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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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- Methods for formation of aryl-sulfur and aryl-selenium compounds using copper(I) catalysts
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A mild, palladium-free synthetic protocol for the cross-coupling reaction of vinyl or aryl iodides and thiols or selenols using, in certain embodiments, 10 mol % CuI and 10 mol % neocuproine, with NaOt-Bu as the base, in toluene at 110 ° C. A variety of vinyl/aryl sulfides and vinyl/aryl selenides can be synthesized in excellent yields from readily available iodides and thiols or selenols.
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Page/Page column 7-8; 23
(2008/06/13)
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- A general method for the formation of aryl-sulfur bonds using copper(I) catalysts.
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[reaction: see text] We report a mild, palladium-free synthetic protocol for the cross-coupling reaction of aryl iodides and thiols using 10 mol % CuI and 10 mol % neocuproine, with NaOt-Bu as the base, in toluene at 110 degrees C. Using this protocol, we have shown that a variety of aryl sulfides can be synthesized in excellent yields from readily available iodides and thiols.
- Bates, Craig G,Gujadhur, Rattan K,Venkataraman
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p. 2803 - 2806
(2007/10/03)
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- A SIMPLE PREPARATION OF SYMMETRICAL AND UNSYMMETRICAL DIARYL SULFIDES FROM ARENEDIAZONIUM TETRAFLUOROBORATES
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The reaction between arenediazonium tetrafluoroborates and arenethiolates in Me2SO represents a mild, efficient and safe alternative to the Ziegler synthesis of diaryl sulfides.
- Petrillo, Giovanni,Novi, Marino,Garbarino, Giacomo,Dell'Erba, Carlo
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p. 6365 - 6368
(2007/10/02)
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- PREPARATION OF PHENYL ARYL SULFIDES BY REACTION OF BENZYNE WITH ETHYL ARYL SULFIDES
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A variety of ethyl aryl sulfides (1) react with benzyne, with evolution of ethylene, to give phenyl aryl sulfides (3) in excellent yields, thus providing a general synthesis of 3 from arenethiols since 1 are quantitatively obtainable from arenethiols and ethyl bromide.
- Nakayama, Juzo,Fujita, Toko,Hoshino, Masamatsu
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p. 249 - 250
(2007/10/02)
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