- Homoleptic and heteroleptic Zn(ii) selone catalysts for thioetherification of aryl halides without scrubbing oxygen
-
Five new mononuclear tetra-coordinated zinc(ii) selones, [Zn(L1)2Cl2] (1), [Zn(L1)2Br2] (2), [{Zn(L2)4}{BF4}2] (3), [{Zn(L2)4}{ClO4}2] (4), and [Zn(L2)2Br2] (5), have been isolated from a one-pot reaction between the corresponding zinc(ii) salt and selone ligand, 1-methyl 3-naphthylmethylimidazoline-2-selone (L1) or 1-isopropyl 3-methylimidazoline-2-selone (L2). All these complexes were characterized by CHN analysis, FT-IR, NMR studies, and single-crystal X-ray crystallography techniques. The Zn(ii) center in 1-5 exhibits a distorted tetrahedral geometry. Besides, 1-5 were employed as catalysts in the thioetherification of aryl halides. The first zinc(ii) catalyst-mediated thioetherification of aryl halides without scrubbing oxygen was demonstrated. Catalysts 1-5 are highly active towards the cross-coupling reaction between aryl halides and thiophenols. The catalytic ability of 1-5 was explored in THF, toluene, and CH3CN solvents with different bases such as K2CO3, Cs2CO3, and NaOtBu. Interestingly, the zinc(ii) center attached to two selone ligands is much more catalytically active than that attached to four selone ligands.
- Vaddamanu, Moulali,Velappan, Kavitha,Prabusankar, Ganesan
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p. 3574 - 3583
(2020/03/17)
-
- CuMoO4 Bimetallic Nanoparticles, An Efficient Catalyst for Room Temperature C?S Cross-Coupling of Thiols and Haloarenes
-
CuII catalyst is less efficient at room temperature for C?S cross-coupling. C?S cross-coupling by CuII catalyst at room temperature is not reported; however, doping of copper with molybdenum metal has been realized here to be more efficient for C?S cross-coupling in comparison to general CuII catalyst. The doped catalyst CuMoO4 nanoparticle is found to be more efficient than copper. The catalyst works under mild conditions without any ligand at room temperature and is recyclable and effective for a wide range of thiols and haloarenes (ArI, ArBr, ArF) from milligram to gram scale. The copper-based bimetallic catalyst is developed and recognized for C?S cross-coupling of haloarenes with alkyl and aryl thiols.
- Panigrahi, Reba,Sahu, Santosh Kumar,Behera, Pradyota Kumar,Panda, Subhalaxmi,Rout, Laxmidhar
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p. 620 - 624
(2019/12/27)
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- Bimetallic BaMoO4 nanoparticles for the C-S cross-coupling of thiols with haloarenes
-
We disclosed new bimetallic BaMoO4 nanoparticles for the C-S cross-coupling reaction. The C-S cross-coupling reaction of alkyl/aryl thiols with haloarenes was accomplished with high yields. The reaction has good functional group tolerance and selectivity. This is an efficient protocol for synthesizing the building blocks of pharmaceuticals containing C-S bonds. The catalyst is recyclable. The unactivated bromo- and 4-acetyl fluoro-arenes can well couple to afford thioethers in high yields. The reaction is believed to proceed by oxidative addition and reductive elimination.
- Panda, Subhalaxmi,Sahu, Santosh Kumar,Behera, Pradyota Kumar,Panigrahi, Reba,Garnaik, Bamakanta,Rout, Laxmidhar
-
supporting information
p. 2500 - 2504
(2020/02/20)
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- Pd (II) immobilized on clinoptilolite as a highly active heterogeneous catalyst for ullmann coupling-type s-arylation of thiols with aryl halides
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Background: There are a number of protocols for Ullmann coupling–type S-arylation reactions, many of them suffer from the use of homogenous and often corrosive catalyst, cumbersome workup procedures, and long reaction times. Besides, many of these reagents are expensive and non-recoverable, leading to the generation of a large amount of toxic waste particularly when large-scale applications are considered. Objective: The aim of this study was to prepare a new Pd catalyst bonded on the surface of zeolite as a heterogeneous catalyst. Methods: A heterogeneous palladium catalyst has been prepared by immobilizing Pd ions on Clinoptilolite. This novel developed heterogeneous catalyst was thoroughly examined for Ullmann coupling–type S-arylation reaction using different bases, solvents and 0.003 mg of the catalyst. The structural and morphological characterizations of the catalyst were carried out using XRD, TGA, BET and TEM techniques. Results: Highly efficient heterogeneous palladium catalyst has been developed by immobilizing Pd ions on Clinoptilolite, as one of the most abundant naturally occurring zeolites for Ullmann S-arylation. By using this method, we provide an efficient way to a wide variety of substituted thiolic compounds. Moreover, the catalyst is easily recovered using simple filtration and reused for 5 consecutive runs. Conclusion: In this effort, we developed a new Pd catalyst bonded on the surface of zeolite as a substrate to prepare the heterogeneous catalyst. We demonstrate that this novel catalyst offers reliable and convincing data that may offer a valuable application in further developing the science and technology of Ullmann reaction protocols and allied industries. Additionally, the catalyst was reusable and kept its high activities over a number of cycles.
- Alizadeh, Abdollah,Khalilzadeh, Mohammad A.,Alipour, Eskandar,Zareyee, Daryoush
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p. 657 - 666
(2020/08/24)
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- Highly active mesoionic chalcogenone zinc(II) derivatives for C-S cross-coupling reactions
-
The first mesoionic heavier chalcogenones, L1-L3 [L1 = 1-(2-mesitylene)-3-methyl-4-phenyltriazolin-5-selone; L2 = 1-(2-mesitylene)-3-methyl-4-phenyltriazolin-5-thione; L3 = 1-(benzyl)-2-3(methyl)-4-phenyltriazolin-5-selone], were isolated and characterised. Density functional theory was used to obtain insights into the σ donor and π accepting nature of mesoionic chalcogenones. Using these new ligands, a series of the first zinc(ii) mesoionic chalcogenone complexes were isolated. Three mono nuclear zinc(ii) chalcogenone complexes, [(L1)Zn(Cl)2(HOMe)] (1), [(L2)Zn(Cl)2(HOMe)] (3) and [(L2)Zn(Br)2(HOMe)] (4), and two dinuclear zinc complexes, [(L1)Zn(Br)(μ2-Br)]2 (2) and [(L3)Zn(Br)(μ2-Br)]2 (5), containing mesoionic thione and selone ligands were synthesized and characterised. These new complexes 1-5 represent the first structurally characterized mesoionic chalcogenone supported metal derivatives. Furthermore, all zinc complexes were characterized by thermogravimetric analysis and UV-vis spectroscopy. The solid-state structures of all zinc complexes were determined by single-crystal X-ray diffraction. The catalytic activities of the zinc(ii) complexes in thioetherification reactions were investigated without scrubbing of oxygen. The scope of the catalytic reactions was explored with a wide range of thiophenols and aryl halides. The diaryl thioethers were obtained in very good yield under mild conditions. The present protocol furnishes a synthetic route for the C-S cross-coupling of thiophenols and aryl halides without scrubbing oxygen and moisture.
- Vaddamanu, Moulali,Prabusankar, Ganesan,Velappan, Kavitha
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p. 129 - 140
(2019/12/26)
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- CuI-catalyzed direct synthesis of diaryl thioethers from aryl boronic acids and arylsulfonyl chlorides
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A CuI-catalyzed direct coupling of aryl boronic acids with arylsulfonyl chlorides for the preparation of diaryl thioethers was developed. The reaction is initiated by a PPh3 reduction of the arylsulfonyl chloride, followed by a CuI-catalyzed C–S coupling with an aryl boronic acid. Various arylsulfonyl chlorides can directly serve as a sulfur source in this mild and efficient reaction giving the desired products in moderate to good yields. Moreover, this practical method has also been applied to the thioetherification of aryl iodides and acetylacetones.
- Huang, Keke,Yang, Min,Lai, Xiao-Jing,Hu, Xin,Qiu, Guanyinsheng,Liu, Jin-Biao
-
-
- Surfactant-Type Catalyst for Aerobic Oxidative Coupling of Hydrazine with Thiol in Water
-
A series of PEG-functionalized nitrogen ligands were developed to conduct an aerobic oxidative cross-coupling reaction between alkyl- or aryl-hydrazines with thiols in water. This surfactant-type catalyst enables high efficiencies and selectivities, while tolerating a large variety of functional groups. The mother liquor is still catalytically active after five runs.
- Ren, Xuanhe,Tang, Shanyu,Li, Longjia,Li, Jiao,Liang, Helong,Li, Ganzhong,Yang, Guanyu,Li, Heng,Yuan, Bingxin
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p. 8683 - 8690
(2019/07/08)
-
- C-S coupling with nitro group as leaving group via simple inorganic salt catalysis
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An efficient and practical synthetic protocol to synthesize nonsymmetrical aryl thioethers by nucleophilic aromatic substitution (SNAr) reaction of nitroarenes by thiols with potassium phosphate as the catalyst is described. Various moderate to strong electron-withdrawing functional groups are tolerated by the system to provide thioethers in a good to excellent yields. We also showed that the present method allows access to 3 drug examples in a short reaction time. Finally, mechanistic studies suggest that the reaction may form the classic Meisenheimer complex through a two-step addition-elimination mechanism.
- Xuan, Maojie,Lu, Chunlei,Lin, Bo-Lin
-
supporting information
(2019/08/26)
-
- Cerium catalyst promoted C-S cross-coupling: Synthesis of thioethers, dapsone and RN-18 precursors
-
In this work, we present a novel, efficient and green methodology for the synthesis of thioethers by the C-S cross-coupling reaction with the assistance of [Ce(l-Pro)2]2Ox as a heterogeneous catalyst in good to excellent yields. A scale-up of the protocol was explored using an unpublished methodology for the synthesis of a dapsone-precursor, which proved to be very effective over a short time. The catalyst [Ce(l-Pro)2]2Ox was recovered and it was shown to be effective for five more reaction cycles.
- Tavares Junior, José M. Da C.,Da Silva, Caren D. G.,Dos Santos, Beatriz F.,Souza, Nicole S.,De Oliveira, Aline R.,Kupfer, Vicente L.,Rinaldi, Andrelson W.,Domingues, Nelson L. C.
-
supporting information
p. 10103 - 10108
(2019/12/23)
-
- An efficient protocol for the synthesis of thioethers via iron-catalyzed cross-coupling reaction and its mechanistic investigation
-
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
-
p. 270 - 276
(2018/11/26)
-
- Lewis Base/Bronsted Acid Dual-Catalytic C-H Sulfenylation of Aromatics
-
A Lewis base/Bronsted acid catalyzed aromatic sulfenylation is reported. These studies demonstrated that the incorporation of electron-rich sulfenyl groups proceeded in the absence of a Lewis base, with kinetic studies indicating an autocatalytic mechanism. The incorporation of electron-poor sulfenyl groups demonstrated little autocatalysis necessitating the use of a Lewis base. This method proved amenable to diverse arenes and heterocycles and was effective in the context of the late-stage functionalization of biologically active small molecules.
- Nalbandian, Christopher J.,Brown, Zachary E.,Alvarez, Erik,Gustafson, Jeffrey L.
-
supporting information
p. 3211 - 3214
(2018/06/11)
-
- SMALL MOLECULE ACTIVATORS OF NICOTINAMIDE PHOSPHORIBOSYLTRANSFERASE (NAMPT) AND USES THEREOF
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Provided herein are small molecule activators of Nicotinamide Phosphoribosyltransferase (NAMPT), compositions comprising the compounds, and methods of using the compounds and compositions.
- -
-
Paragraph 00637; 00667
(2018/08/03)
-
- Palladium-Catalyzed Oxidative Cross-Coupling of Arylhydrazines and Arenethiols with Molecular Oxygen as the Sole Oxidant
-
A highly efficient palladium-catalyzed oxidative cross-coupling of arylhydrazines and arenethiols with molecular oxygen as the sole oxidant to afford unsymmetrical diaryl sulfides has been developed. The only byproducts are nitrogen and water. A broad range of functional groups, even the reactive iodides, are tolerated and thus offer the opportunity for further functionalization.
- Wang, Changliu,Zhang, Zhenming,Tu, Yongliang,Li, Ying,Wu, Jiale,Zhao, Junfeng
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p. 2389 - 2394
(2018/02/23)
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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
-
supporting information
p. 2918 - 2921
(2017/03/15)
-
- Room-Temperature Arylation of Thiols: Breakthrough with Aryl Chlorides
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The formation of aryl C?S bonds is an important chemical transformation because aryl sulfides are valuable building blocks for the synthesis of biologically and pharmaceutically active molecules and organic materials. Aryl sulfides have traditionally been synthesized through the transition-metal-catalyzed cross-coupling of aryl halides with thiols. However, the aryl halides used are usually bromides and iodides; readily available, low-cost aryl chlorides often not reactive enough. Furthermore, the deactivation of transition-metal catalysts by thiols has forced chemists to use high catalyst loadings, specially designed ligands, high temperatures, and/or strong bases, thus leading to high costs and the incompatibility of some functional groups. Herein, we describe a simple and efficient visible-light photoredox arylation of thiols with aryl halides at room temperature. More importantly, various aryl chlorides are also effective arylation reagents under the present conditions.
- Jiang, Min,Li, Haifang,Yang, Haijun,Fu, Hua
-
supporting information
p. 874 - 879
(2017/01/14)
-
- Diaryl thioether compound, and synthetic method and application thereof
-
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.
- -
-
Paragraph 0055-0059
(2018/02/04)
-
- A quick Chan-Lam C-N and C-S cross coupling at room temperature in the presence of square pyramidal [Cu(DMAP)4I]I as a catalyst
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A rapid and efficient protocol for C-N and C-S cross coupling has been developed using a new square pyramidal copper complex, [Cu(DMAP)4I]I. The complex was successfully synthesized via a disproportionation reaction of CuI and DMAP in DMSO. The catalytic activity of the complex was found to be excellent for Chan-Lam coupling reaction between aryl boronic acid and amine, amide, azide or thiol. The reaction could be carried out in the presence of only 2 mol% of the copper catalyst in methanol at room temperature within a short time.
- Roy, Subhasish,Sarma, Manas Jyoti,Kashyap, Bishwapran,Phukan, Prodeep
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supporting information
p. 1170 - 1173
(2016/01/15)
-
- Iridium and phosphine promoted C-F bond activation: The C-S cross-coupling of aryl fluorides with diaryl disulfides to synthesize thioethers
-
Carbon-fluorine bond is the strongest known single bond to carbon and proved very difficult to cleave. An iridium and phosphine promoted C-F bond activation was developed, for the first time achieving the C-S cross-coupling reaction of disulfides with aryl fluorides using iridium complex. The corresponding monoarylthiolation products were obtained at moderate to good yields. Thus, it represents a new method for the synthesis of aryl sulfides through C-F bond activation.
- Li, Liang,Miao, Hongyan,Ding, Yuqiang
-
supporting information
p. 6405 - 6408
(2015/11/16)
-
- Ascorbic Acid Promoted Metal-Free Synthesis of Aryl Sulfides with Anilines Nitrosated in Situ by tert -Butyl Nitrite
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A mild, metal-free synthesis of aryl sulfides has been disclosed. Aryl diazonium ion was generated by the in situ nitrosation of aniline, and it was reduced by ascorbic acid (vitamin C) to form aryl radical, which underwent a thiolation with disulfide to yield aryl sulfide. The reaction proceeded smoothly without heating or irradiation. This strategy was also expanded to the synthesis of aryl selenides.
- Bu, Mei-Jie,Lu, Guo-Ping,Cai, Chun
-
supporting information
p. 1841 - 1846
(2015/08/06)
-
- 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
-
supporting information
p. 928 - 932
(2015/03/30)
-
- 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
-
supporting information
p. 4923 - 4926
(2015/07/28)
-
- 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)
-
- Maghemite-Copper Nanocomposites: Applications for Ligand-Free Cross-Coupling (C-O, C-S, and C-N) Reactions
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A magnetically retrievable, efficient, and benign maghemite-Cu nanocatalyst was synthesized from inexpensive precursors and applied for C-O, C-N, and C-S bond-formation reactions. The obtained maghemite-Cu nanocatalyst was characterized by various techniques such as XRD, X-ray photoelectron spectroscopy, field-emission gun SEM with energy-dispersive spectroscopy, atomic absorption spectroscopy, TEM, high-angle annular dark-field scanning transmission electron microscopy, FTIR spectroscopy, and M?ssbauer spectroscopy. Excellent catalytic activity, ease of recovery, and reusability without a significant loss of yield make the present protocol highly sustainable to deal with industrial and environmental concerns. Magnetic attraction: A magnetically retrievable, efficient, and benign maghemite-Cu nanocatalyst is synthesized from inexpensive precursors and applied for C-O, C-N, and C-S bond-formation reactions. Excellent catalytic activity, ease of recovery, and reusability without significant loss of yield make the present protocol highly sustainable to deal with industrial and environmental concerns.
- Sharma, Rakesh K.,Gaur, Rashmi,Yadav, Manavi,Rathi, Anuj K.,Pechousek, Jiri,Petr, Martin,Zboril, Radek,Gawande, Manoj B.
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p. 3495 - 3502
(2015/11/10)
-
- Development of a robust process for the preparation of high-quality dicyclopropylamine hydrochloride
-
A short and efficient process for the preparation of high-quality dicyclopropylamine HCl salt is described. An oxygen-mediated Chan-Lam coupling of N-cyclopropyl 4-nitrobenzenesulfonamide with cyclopropylboronic acid was followed by an optimized p-nosyl deprotection with 1-decanethiol, providing the title compound in high chemical yield. This process addresses many of the challenges and liabilities inherent in previous synthetic approaches to this challenging molecule. The collection of key safety data enabled implementation of an oxygen-mediated process on-scale and ensured safe operation throughout development, optimization, and processing.
- Mudryk, Boguslaw,Zheng, Bin,Chen, Ke,Eastgate, Martin D.
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p. 520 - 527
(2014/05/06)
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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)
-
- KF/clinoptilolite: An efficient promoter for the synthesis of thioethers
-
Potassium fluoride impregnated on natural zeolite as a new solid base system effectively catalyzes the coupling of thiophenols with electron-deficient fluoro-, chloro- and bromo-arenes in DMSO. This versatile and efficient solid base has been demonstrated to afford the corresponding desired products in good to excellent yields. This procedure provides a convenient, efficient and practical method for the preparation of diaryl thioethers.
- Salmanpour, Sadegh,Khalilzadeh, Mohammad A.,Hosseini, Abolfazl
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p. 339 - 344
(2013/07/28)
-
- Ionic liquid as base and phase transfer agent: A green protocol for the synthesis of diaryl sulphides in water
-
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)
-
- Microwave-assisted reaction of aryl diazonium fluoroborate and diaryl dichalcogenides in dimethyl carbonate: A general procedure for the synthesis of unsymmetrical diaryl chalcogenides
-
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)
-
- Design, synthesis and antitumor activity of novel cis-furoquinoline derivatives
-
A series of novel cis-furoquinoline derivatives was synthesized and tested for their antitumor activities in vitro against HepG2 cells, Lu-04 cells and Leu02 cells to evaluate structure-activity relationships. Assay-based antiproliferative activity study revealed that several compounds had significant effects on cytotoxicity, among which compounds 2f, 2l, 2q were found to be the most active compounds. Above all, compounds 2f, 2l, 2q would be potential anticancer agents which deserved further research.
- Li, Jie,Pei, Shuchen,Zhu, Yingxi,Wu, Jianbo,Chen, Yin,Zhang, Weiyu,Wu, Yong
-
experimental part
p. 379 - 388
(2012/07/03)
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- Microwave-assisted Ullmann-Buchwald C-S bond formation using a copper(I) catalyst and trans-cyclohexane-1,2-diol as ligand
-
Microwave irradiation of a thiophenol or alkyl thiol (1 equiv.) and an aryl halide (1 equiv.) in 2-propanol at 120°C for three hours in the presence of K2CO3 (2 equiv.) as base using copper(I) iodide as catalyst (5 mol%) and trans-cyclohexane-1,2-diol (2 equiv.) as ligand provides a rapid and convenient method for C-S bond formation. The process is most efficient using thiophenol and aryl iodide precursors, both of which may contain electron-donating and electronwithdrawing groups, to give the corresponding diaryl sulfide in good to excellent yield. ARKAT-USA, Inc.
- Bagley, Mark C.,Fusillo, Vincenzo,Hills, Edward G.B.,Mulholland, Alex T.,Newcombe, Joseph,Pentecost, Leanne J.,Radley, Emily L.,Stephens, Bethan R.,Turrell, Christopher C.
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p. 294 - 313
(2013/01/16)
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- A highly efficient method for the copper-catalyzed selective synthesis of diaryl chalcogenides from easily available chalcogen sources
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An efficient protocol for copper-catalyzed C-S or C-Se bond formation between aryl iodides and easily available chalcogen sources leading to diaryl chalcogenides is reported. A variety of symmetrical diaryl sulfides and diaryl selenides were synthesized in good to excellent yields. Unsymmetrical diaryl sulfides were also obtained in moderate yields from two different aryl iodides by a one-pot tandem process. This strategy was further successfully utilized for the synthesis of 2-phenylbenzo[b]thiophene and of [1]benzothieno[3,2-b] benzothiophene. A new Cu-catalyzed one-pot approach for the selective synthesis of symmetrical diaryl chalcogenides and unsymmetrical diarylsulfides with use of Na2S or Se as chalcogen sources has been developed. Copyright
- Li, Yaming,Nie, Caiping,Wang, Huifeng,Li, Xiaoying,Verpoort, Francis,Duan, Chunying
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p. 7331 - 7338
(2012/01/06)
-
- Substitution reactions between arenethiolate anions and 1,3-dihalo-2,2-dimethylpropanes. Synthetic scope and mechanistic aspects
-
The synthetic scope of the reactions between benzenethiolate, 4-methoxybenzenethiolate, 2-naphthalenethiolate, and 2-pyridinethiolate anions with 1,3-dihalo-2,2-dimethylpropane was studied. These reactions render mono and disubstituted products from good
- Barrionuevo, Cecilia A.,Argueello, Juan E.,Penenory, Alicia B.
-
experimental part
p. 245 - 259
(2011/06/19)
-
- Microwave-assisted cross-coupling for the construction of diaryl sulfides
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The construction of diaryl sulfides through the cross-coupling of aryl iodides and thiols in microwave heating is described. By using this method, a variety of diaryl sulfides can be prepared in a mild condition and in high yields. Deactivated 4-nitrothiophenol was effective to afford the product in 94% yield. Sterically hindered ortho-substituted aryl iodides or thiophenols provided diaryl sulfides effectively by this microwave-assisted coupling reaction.
- Tan, Chen-Ming,Chen, Grace Shiahuy,Chena, Chien-Shu,Chern, Ji-Wang
-
experimental part
p. 94 - 100
(2011/11/06)
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- Synthesis of aryl sulfides by decarboxylative C-S cross-couplings
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A study was conducted to demonstrate the transition-metal-catalyzed synthesis of aryl sulfides by decarboxylative C-S cross-couplings. Coupling reaction of 2-nitrobenzoic acid with 1-octanethiol were carried in the presence of different combinations of tr
- Duan, Zhongyu,Ranjit, Sadananda,Zhang, Pengfei,Liu, Xiaogang
-
supporting information; experimental part
p. 3666 - 3669
(2009/12/07)
-
- Copper(I)-catalyzed S-arylation of thiols with activated aryl chlorides on water
-
Copper chloride-catalyzed S-arylation of arenethiols is effected with activated aryl chlorides in neat water by using ethylenediamine as the pair ligand/base. This convenient, environmentally more friendly procedure for the coupling of aryl chlorides allows the arylation between sterically demanding coupling partners.
- Herrero, María Teresa,SanMartin, Raul,Domínguez, Esther
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experimental part
p. 1500 - 1503
(2009/05/07)
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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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- Efficient ligand-free nickel-catalyzed C-S cross-coupling of thiols with aryl iodides
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NiCl2·6H2O efficiently catalyzes the C-S bond formation by the cross-coupling of aryl iodides with thiols in tetrabutylammonium bromide (TBAB) in excellent yield. The reaction functions in air and the NiLn-TBAB can be recovered and recycled without the loss of activity.
- Jammi, Suribabu,Barua, Priyanka,Rout, Laxmidhar,Saha, Prasenjit,Punniyamurthy, Tharmalingam
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p. 1484 - 1487
(2008/09/18)
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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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- Simple and efficient recyclable catalytic system for performing copper-catalysed S-arylation reactions in the presence of water
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A novel protocol for the copper-catalysed S-arylation of thiophenol derivatives with aryl halides leading to diaryl sulfides is reported. The reactions were catalysed by a combination of a copper salt and a 1,2-diamine derivative (acting both as the ligand and as the base) using exclusively water as the solvent. The recovery and successful reutilisation of the aqueous medium containing the active catalyst is described. Furthermore, one example of a "one-pot" process involving Br/I exchange of an aryl bromide and further S-arylation is presented.
- Carril, Monica,SanMartin, Raul,Dominguez, Esther,Tellitu, Imanol
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p. 5100 - 5105
(2008/02/09)
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- THIOPHENYLAMINOIMIDAZOLINES
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Methods for treatment of IP antagonist mediated diseases or conditions by administration to a subject in need thereof a compound of formula (I) wherein R1, R 2 , A and X are as defined herein. Also disclosed are compounds and related compositions.
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Page/Page column 29
(2010/02/10)
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- Discovery and SAR development of 2-(phenylamino) imidazolines as postacyclin receptor antagonists
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On the basis of screening hits (1a,b), a series of selective, high affinity prostacyclin receptor antagonists was developed. The optimized lead compound 25d [(4,5-dihydro-1H-imidazol-2-yl)-[4-(4-isopropoxybenzyl)phenyl] amine] had analgesic activity in the rat.
- Clark, Robin D.,Jahangir, Alam,Severance, Daniel,Salazar, Rick,Chang, Thomas,Chang, David,Jett, Mary Frances,Smith, Steven,Bley, Keith
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p. 1053 - 1056
(2007/10/03)
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- Synthesis of diaryl ethers, diaryl thioethers, and diarylamines mediated by potassium fluoride-alumina and 18-crown-6: Expansion of scope and utility
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An efficient alternative to the Ullmann ether synthesis of diaryl ethers, diaryl thioethers, and diarylamines involving the S(N)Ar addition of a phenol, thiophenol, or aniline to an appropriate aryl halide, mediated by potassium-fluoride alumina and 18-crown-6 in acetonitrile or DMSO, is described. Expansion of the reaction conditions to include DMSO as solvent has resulted in a far greater range of substitution patterns permitted on the electrophile. For example, it was found that electronically unfavorable 3- chlorobenzonitrile could be condensed with 3-methoxyphenol to form the corresponding diaryl ether in 66% yield, a combination not normally amenable to Ullmann coupling. Electron-withdrawing groups present on the electrophile may be as diverse as nitro, cyano, formyl, acetyl, ester, amide, and even aryl. The method features a simple reaction procedure that provides products in generally good to excellent purified yields.
- Sawyer, J. Scott,Schmittling, Elisabeth A.,Palkowitz, Jayne A.,Smith III, William J.
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p. 6338 - 6343
(2007/10/03)
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- Arene sulfenylation by arenesulfenamides and arenesulfenylacetates
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Two systems for arene sulfenylation were investigated: arenesulfenamides in the presence of SO3 and sulfenylacetate complexes with AlBr3.A preference for the second reagent was demonstrated for sulfenylation of substrates bearing donor substituents. - Key words: arenesulfenamides; arenesulfenylacetates; diarenesulfides.
- Zefirov, N. S.,Zyk, N. V.,Beloglazkina, E. K.,Tyurin, V. S.
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p. 315 - 317
(2007/10/02)
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- MOLECULAR POLARIZABILITY OF ORGANIC COMPOUNDS AND THEIR COMPLEXES. XLIV. CONFORMATIONS OF DIARYL SULFONES IN DIOXANE
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We determined molar Kerr constants and dipole moments in dioxane solutions for a number of diaryl sulfones with various substituents in the aromatic nuclei.The data obtained were analyzed to establish the preferential molecular conformations.It was shown that diaryl sulfones occur in solution mainly in the form of orthogonal or planar-orthogonal conformers, or as an equilibrium between these two.In the orthogonal conformer both aromatic rings are perpendicular to the plane of the CArSCAr bonds, whereas in the planar-orthogonal conformer one ring is coplanar and the other orthogonal to this plane.The orthogonal orientation of aromatic rings relative to the CArSCAr plane originates from the ?-conjugation of the nuclei and the sulfonyl gruop of the sulfone molecules.
- Bulgarevich, S. B.,Movshovich, D. Ya.,Ivanova, N. A.,Filippov, S. E.,Finocchiaro, P.,Failla, S.
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p. 379 - 387
(2007/10/02)
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- Conformational investigation of diarylsulphides by Kerr effect and dipole moment methods
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Molar Kerr constants and electric dipole moments are reported for (4-NO2C6H4)2S, (4-MeOC6H4)2S, (4-MeOC6H4)(4'-NO2C6H4)S, (2-MeOC6H4)(4'-NO2C6H4)S, (4-MeOC6H4)(2'-NO2C6H4)S, (2-MeOC6H4)(2'-NO2C6H4)S and (4-ClC6H4)2SO as solutes in dioxane at 298 K.The data are analysed in terms of the preferred conformations adopted in solution.In most cases these data are consistent with the presence, in dioxane, of helical conformers, where both aromatic rings are twisted in the same direction with respect to the CAr-S-CAr molecular reference plane.The (4-ClC6H4)2SO molecule adopts an orthogonal conformation where both aryl rings are approximately perpendicular to the CAr-S-CAr molecular reference plane.
- Bulgarevich, S. B.,Movshovich, D. Ya.,Ivanova, N. A.,Finocchiaro, P.,Failla, S.
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p. 207 - 222
(2007/10/02)
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- Conformational investigation of diarylsulphones by Kerr effect and dipole moment methods
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Molar Kerr constants and electric dipole moments are reported for (C6H5)2SO2, (4Cl-C6H4)(C6H5)SO2, (2,4,6-Me3C6H2)(4'-Br-C6H4)SO2, (4-NO2C6H4)2SO2, (4-MeOC6H4)(4'-NO2C6H4)SO2, (2-MeOC6H4)(4'-NO2C6H4)SO2, (2-NO2C6H4)(4'-MeOC6H4)SO2 and (2-MeOC6H4)(2'-NO2C6H4)SO2 as solutes in dioxane solution at 298 K.The data are analysed in terms of the preferred conformations adopted in solution.In most cases these data are consistent with the presence, in dioxane, of orthogonal or planar-orthogonal conformers, or of a mixture of them.In the orthogonal rotamer both aromatic rings are approximately perpendicular to the CAr-S-CAr molecular reference plane whereas in the planar-orthogonal conformer one ring is coplanar and the other is orthogonal to the reference CAr-S-CAr plane.
- Bulgarevich, S. B.,Movshovich, D. Ya.,Ivanova, N. A.,Filippov, S. E.,Finocchiario, P.,Failla, S.
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p. 365 - 376
(2007/10/02)
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- KINETIC RELATIONSHIPS OF THE REACTION OF 4-NITROHALOGENOBENZENES WITH SUBSTITUTED POTASSIUM THIOPHENOLATES
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The kinetic relationships governing the substitution of the halogen atom in 4-nitrohalogenobenzenes by a phenylthio group were studied, and the kinetic and thermodynamic parameters of the process were determined.A quantitative assessment of the sensitivity of the reaction to the effect of the substituent in the reagent and the leaving group of the substrate is given.It is concluded that a two-stage SNAr "addition-elimination" mechanism is realized.
- Nikiforov, A. V.,Alov, E. M.,Moskvichev, Yu. A.,Mironov, G. S.,Kryukova, G. G.,Smirnova, T. M.
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p. 933 - 936
(2007/10/02)
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- NMR Study of Substituent Effects in 4-Substituted and 4,4'-Disubstituted Diphenyl Sulphides
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The proton and carbon NMR spectra of nine 4-X-diphenyl sulphides (series 1), seven 4-X-4'-NO2-diphenyl sulphides (series 2) and eight 4,4'-X2-diphenyl sulphides (series 3) have been obtained.Correlation of the 13C chemical shifts with the appropriate substituent chemical shifts (SCS) for monosubstituted benzenes (Lynch plots) show an enhancement of substituent effect at C-1 (carbon para to the substituent) in series 1 ans 2, but not in series 3.The carbons of the unsubstituted ring in series 1 also correlate with Cp-SCS, with slopes of less than unity; correlation for C-1' has a negative slope.Dual substituent parameter (DSP) correlations of the 13C chemical shifts with ?I/?oR are good to exellent for all the carbons of series 1 compounds, except those ortho to the substituent X.The carbons meta to the substituent X correlate well, but with negative values for ρI and ρR, although showing a scattered Lynch plot.Similar correlations are found with some carbon shifts in series 2, and with C-1 shifts in series 3.It is concluded that (a) reverse resonance effects are operative at the position meta to the variable substituent by virtue of the sulphur substituent ortho to that carbon; (b) there is transmission of inductive (field) and resonance effects from one aryl ring to the other, except when both rings carry substituents of the same electronic character (series 3); (c) there is some evidence for ?-polarization in the unsubstituted phenyl ring of series 1 compounds.Key words 1H NMR 13C NMR Diphenyl sulphides substituent effects
- Chandrasekaran, R.,Perumal, S.,Wilson, D.A.
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p. 1001 - 1006
(2007/10/02)
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- Pyridine N-Sulphides. Some Simple N-Arylthiopyridinium Salts and a Possible Source of Arylsulphenium Ions
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N,N'-Dipyridinium disulphide dichloride (1) and 1-(4-nitrophenylthio)pyridinium chloride (5) and its 4-NMe2 derivative (2) have been synthesized and their structures established unambiguously; they undergo nucleophilic attack at sulphur rather than in the
- Abramovitch, Rudolph A.,Miller, Adrian L.,Pilski, Jacek
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p. 703 - 704
(2007/10/02)
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- NN-Diacyl Arylsulphenamides as an Unambiguous and Convenient Source of Arylsulphenium Ions
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Singlet p-nitrophenylsulphenium ions can be generated conveniently from the readily available NN-diacetyl-p-nitrophenylsulphenamide and trifluoroacetic acid, as confirmed by kinetic studies; it adds stereospecifically to olefins and substitutes into anisole quantitatively.
- Abramovitch, Rudolph A.,Pilski, Jacek
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p. 704 - 705
(2007/10/02)
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