- 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)
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- Ni-catalyzed C–S bond cleavage of aryl 2-pyridyl thioethers coupling with alkyl and aryl thiols
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A nickel-catalyzed C–SPy bond activation reactions to produce a variety of thioethers has been developed. The reaction is promoted by a user-friendly, inexpensive, air and moisture-stable Ni precatalyst. Various aryl 2-pyridyl thioethers and a wide range of alkyl and aryl thiols substrates were tolerated in this process which afforded products in moderate to excellent yields.
- Wang, Cheng-Yi,Tian, Rui,Zhu, Yong-Ming
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- 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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- 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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- Electrochemical Thiolation and Borylation of Arylazo Sulfones with Thiols and B2pin2
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An efficient electrochemical synthesis approach of various unsymmetrical thioethers and arylboronates has been developed. Bench stable arylazo sulfones were used as radical precursors for carbon-heteroatom bond formation under electrochemical conditions. Moreover, the scalability of this approach was evaluated by performing the electrochemical thiolation and borylation of arylazo sulfones with thiols and B2pin2 on a gram scale. This protocol not only avoided the use of stoichiometric oxidants, metal catalysts, activating agents and even added bases, but also exhibited favorable functional group tolerance. (Figure presented.).
- Wang, Rongkang,Chen, Fangming,Jiang, Lvqi,Yi, Wenbin
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supporting information
p. 1904 - 1911
(2021/02/12)
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- An Iodide-Mediated Transition-Metal-Free Strategy towards Unsymmetrical Diaryl Sulfides via Arylhydrazines and Thiols
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A mild, scalable iodine-mediated oxidative cross-coupling reaction of arylhydrazines and thiols for construction of thioethers (sulfides) in the absence of any transition metals or photocatalysts is disclosed. A variety of unsymmetrical diaryl sulfides with broad substrate scope both on thiols and hydrazines were synthesized in high yields in water at room temperature. Furthermore, to demonstrate the utility of the protocol, the above C-S bond formation was applied in the synthesis of the key structure of vortioxetine as an antidepressant drug. The gram-scale outcome also added to the potential utility of this protocol.
- Asadpour, Mohammad,Azizzade, Meysam,Ghasemi, Mehran,Jafarpour, Farnaz,Rajai-Daryasarei, Saideh
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supporting information
p. 727 - 734
(2020/02/25)
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- Direct C-S bond formation: Via C-O bond activation of phenols in a crossover Pd/Cu dual-metal catalysis system
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A dual-metal catalysis system including a newly prepared nanoparticle [SiO2@organic-linker(OL)@Pd(II)] and CuI was introduced with ultra-high catalytic activity (high turnover number (TON), up to 19000) to a one-pot and odorless synthesis of unsymmetrical aryl sulfides by crossover C-S bond formation. The reaction proceeds via C-O bond activation of phenols and direct C-S bond formation in the presence of S8 as an oddorless sulfur source and aryl boronic acids under mild conditions (room temperature). The catalyst could be recycled up to five times without an obvious change in its activity.
- Khakyzadeh, Vahid,Rostami, Abed,Veisi, Hojat,Shirmardi Shaghasemi, Behzad,Reimhult, Erik,Luque, Rafael,Xia, Yuanzhi,Darvishi, Sima
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p. 4491 - 4497
(2019/05/17)
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- Forging C-S Bonds through Nickel-Catalyzed Aryl Anhydrides with Thiophenols: Decarbonylation or Decarbonylation Accompanied by Decarboxylation
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A nickel-catalyzed decarbonylation or decarbonylation accompanied by decarboxylation cross-coupling reaction of aryl anhydrides with thiophenols as coupling partners was disclosed. This method is promoted by a commercially available, moisture-stable, and inexpensive nickel(II) precatalyst. The process can tolerate a variety of functional groups using ubiquitous aryl anhydrides as cross-coupling precursors to produce thioethers in moderate to excellent yields.
- Zhou, Jing-Ya,Tao, Shou-Wei,Liu, Rui-Qing,Zhu, Yong-Ming
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p. 11891 - 11901
(2019/10/11)
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- Iodine-Promoted Tunable Synthesis of 2-Naphthyl Thioethers and 1-Naphthyl Thioethers
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An iodine-promoted regioselective sulfenylation/deoxygenation/aromatization reaction of 1-tetralones with disulfides has been developed. This process could be modified to synthesize 2-naphthyl thioethers and 1-naphthyl thioethers in moderate to excellent
- Bao, Yishu,Yang, Xiuqin,Dai, Zonghao,Ji, Suyu,Zhou, Qingfa,Yang, Fulai
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supporting information
p. 2154 - 2158
(2019/04/13)
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- NiFe2O4 as a magnetically recoverable nanocatalyst for odourless C–S bond formation via the cleavage of C–O bond in the presence of S8 under mild and green conditions
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We present green methodologies for one-pot and odourless syntheses of unsymmetric and symmetric diaryl sulfides via C─O bond activation using NiFe2O4 magnetic nanoparticles as a reusable heterogeneous nanocatalyst. The synthesis of unsymmetric sulfides is performed using the cross-coupling reaction of phenolic esters such as acetates, triflates and tosylates with arylboronic acid/S8 or triphenyltin chloride/S8 as thiolating agents in the presence of base and NiFe2O4 magnetic nanoparticles as a catalyst in poly(ethylene glycol) as solvent at 60–85°C. Also, the synthesis of symmetric diaryl sulfides from phenolic compounds using S8 as the sulfur source and NiFe2O4 as catalyst in dimethylformamide at 120°C is described. Using these protocols, the syntheses of various unsymmetric and symmetric sulfides become easier than using the available protocols due to the use of a magnetically reusable bimetallic nanocatalyst and avoiding the use of thiols and aryl halides.
- Atashkar, Bahareh,Rostami, Amin,Rostami, Abed,Zolfigol, Mohammad Ali
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- Nickel-Catalyzed Thiolation of Aryl Halides and Heteroaryl Halides through Electrochemistry
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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
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supporting information
p. 5033 - 5037
(2019/03/13)
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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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- 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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- 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.
- -
-
Paragraph 0099; 0163; 0164
(2019/01/10)
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- Copper-Catalyzed C-S Bond Formation via the Cleavage of C-O Bonds in the Presence of S8 as the Sulfur Source
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Useful and applicable methods for one-pot and odorless synthesis of unsymmetrical and symmetrical diaryl sulfides via C-O bond activation are presented. First, a new efficient procedure for the synthesis of unsymmetrical sulfides using the cross-coupling reaction of phenolic esters such as acetates, tosylates, and triflates and with arylboronic acid or triphenyltin chloride as the coupling partners is reported. Depending on the reaction, S 8 /KF or S 8 /NaO t -Bu system is found to be an effective source of sulfur in the presence of copper salts and in poly(ethylene glycol) as a green solvent. Then, the synthesis of symmetrical diaryl sulfides from phenolic compounds by using S 8 as the sulfur source and NaO t -Bu in anhydrous DMF at 120 °C under N 2 is described. By these protocols, the synthesis of a variety of unsymmetrical and symmetrical sulfides become easier than the available protocols in which thiols and aryl halides are directly used for the preparation of the sulfides.
- Rostami, Abed,Rostami, Amin,Ghaderi, Arash,Gholinejad, Mohammad,Gheisarzadeh, Sajedeh
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p. 5025 - 5038
(2017/10/06)
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- 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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- Polystyrene resin-supported CuI-cryptand 22 complex: a highly efficient and reusable catalyst for the formation of aryl–sulfur bonds in aqueous media
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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
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supporting information
p. 1625 - 1628
(2018/03/29)
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- By-Product-Catalyzed Redox-Neutral Sulfenylation/Deiodination/Aromatization of Cyclic Alkenyl Iodides with Sulfonyl Hydrazides
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A by-product-catalyzed redox-neutral process has been established through tandem sulfenylation/deiodination/aromatization of cyclic alkenyl iodides with sulfonyl hydrazides. In the absence of external catalysts and additives a range of 4-iodo-1,2-dihydronaphthalenes reacted with sulfonyl hydrazides to give structurally diverse 2-naphthyl thioethers in good yields. Mechanistic studies showed that at an early stage sulfonyl hydrazides decomposed completely to thiosulfonates and disulfides and at a late stage the resulting thiosulfonates underwent tandem sulfenylation/deiodination/aromatization with 4-iodo-1,2-dihydronaphthalenes involving a [1,5]-sigmatropic hydrogen shift. Importantly, iodine was generated as a by-product from 4-iodo-1,2-dihydronaphthalenes upon heating and served as a catalyst for the decomposition of sulfonyl hydrazides and subsequent formation of 2-naphthyl thioethers. (Figure presented.).
- Yang, Fu-Lai,Gui, Yang,Yu, Bang-Kui,Jin, You-Xiang,Tian, Shi-Kai
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supporting information
p. 3368 - 3372
(2016/11/13)
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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
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supporting information
p. 777 - 781
(2016/03/12)
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- 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)
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- 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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- The reaction of grignard reagents with bunte salts: A thiol-free synthesis of sulfides
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S-Alkyl, S-aryl, and S-vinyl thiosulfate sodium salts (Bunte salts) react with Grignard reagents to give sulfides in good yields. The S-alkyl Bunte salts are prepared from odorless sodium thiosulfate by an SN2 reaction with alkyl halides. A Cu-
- Reeves, Jonathan T.,Camara, Kaddy,Han, Zhengxu S.,Xu, Yibo,Lee, Heewon,Busacca, Carl A.,Senanayake, Chris H.
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p. 1196 - 1199
(2014/03/21)
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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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- Silver catalyzed C-C and C-S coupling of aryl halides and thiols with boronic acids
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An efficient Ag(I) catalyzed carbon-carbon and carbon-sulfur bond formation reaction of aryl halides and thiols with boronic acids has been demonstrated. Using this protocol, substrates with a wide range of functional group including electron-rich, and electron deficient substituents have been explored. These reactions are particularly useful to prepare symmetrical and unsymmetrical biphenyls and thioethers. These products were isolated in high yield.
- Das, Rima,Chakraborty, Debashis
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p. 7023 - 7027
(2013/01/15)
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- An efficient, mild and intermolecular ullmann-type synthesis of thioethers catalyzed by a diol-copper(I) complex
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A wide range of diaryl sulfides and aryl alkyl sulfides are synthesized under mild reaction conditions from the corresponding aryl iodides and aromatic/aliphatic thiols through Ullmann-type intermolecular coupling reactions in the presence of catalytic amount of easily available novel trans-9,10-dihydro-9,10-ethanoanthracene-11,12-dimethanol-copper(I) bromide complex at 82 C. The catalytic system is not only capable of coupling electron-withdrawing and electron-releasing substituent-containing substrates, but also tolerates a broad range of functional groups including heteroatom-containing aryl iodides and thiols.
- Prasad,Sekar, Govindasamy
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experimental part
p. 79 - 84
(2010/06/15)
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- Mechanistic insights into C-S cross-coupling reactions catalyzed by nickel bis(phosphinite) pincer complexes
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Nickel bis(phosphinite) pincer complexes [2,6-(R2PO) 2C6H3]NiCl (R = Ph, 1a; R = Me, 1b; R = iPr, 1c; R = tBu, 1d) show catalytic activity in cross-coupling of aryl iodides and aryl thiols. The optimal catalytic conditions involve 1 mol % of 1a and 2 equiv of KOH (with respect to aryl thiols) in DMF at 80 °C and tolerate a variety of functional groups in the substrates. The potential intermediates in these catalytic reactions, such as nickel thiolate complexes [2,6-(Ph2PO)2C6H3]NiSAr (Ar = Ph, 2a; Ar = p-MeC6H4, 3a; Ar = p-MeOC 6H4, 4a), have been synthesized and spectroscopically characterized. The reaction between 2a and PhI in DMF-d7 is slow enough to argue against 2a being directly involved in the C-S bond-forming step. NMR studies suggest that the pincer ligand framework in complexes 1a, 3a, and 4a is destroyed by KOH via the cleavage of P-O bonds to release Ph 2POK, and further decomposition leads to Ph3P and other phosphorus-containing products. The cross-coupling reactions are more effectively catalyzed by Ni(COD)2/Ph2P(O)H. The structures of 1b, 2a, 4a, and [2,6-(Ph2PO)2C6H 3]NiP(O)Ph2 (5a), which is relevant to the decomposition process, have been studied by X-ray crystallography.
- Zhang, Jie,Medley, Christopher M.,Krause, Jeanette A.,Guan, Hairong
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experimental part
p. 6393 - 6401
(2011/02/17)
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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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- Palladium-catalyzed carbon-sulfur cross-coupling reactions with indium tri(organothiolate) and its application to sequential one-pot processes
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(Chemical Equation Presented) It was found that indium tri(organothiolate) is an effective nucleophilic coupling partner in Pd-catalyzed C-S cross-coupling reactions to produce the functionalized sulfides in excellent yields with high atom efficiency and
- Lee, Jae-Young,Phil, Ho Lee
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supporting information; experimental part
p. 7413 - 7416
(2009/05/07)
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- Iron-catalyzed S-arylation of thiols with aryl iodides
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(Chemical Equation Presented) Strike while the iron is hot: An efficient iron-catalyzed protocol for the S-arylation of aromatic and heteroaromatic thiol derivatives has been developed, which involves an inexpensive catalyst system formed by combining FeCl3 and N,N′-dimethylethylenediamine at 135°C. This method avoids the use of expensive and/or air-sensitive ligands and provides in most cases the desired sulfide in high yields.
- Correa, Arkaitz,Carril, Monica,Bolm, Carsten
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p. 2880 - 2883
(2008/12/23)
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