- Synthesis of Aryl Sulfides by Metal-Free Arylation of Thiols with Diaryliodonium Salts under Basic Conditions**
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Metal-free arylation of thiols with diaryliodonium salts has been developed. The application of a strong organic base enables the C?S bond formation under mild and experimentally simple conditions. The method allows for the synthesis of aryl sulfides containing a broad range of aryl groups from an array of thiols, including aryl, heteroaryl, and alkyl ones. The mechanism of the reaction was studied by DFT calculations, demonstrating that it proceeds via the inner sphere pathway involving formation of an Ar2I(SR) intermediate, followed by reductive elimination.
- Kalek, Marcin,Rajkiewicz, Adam A.,Sarkar, Sudeep,Wojciechowska, Natalia
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- Cross-coupling reaction of organoalane reagents with 2-mercaptobenzo-5-membered heterocycles for efficient synthesis of benzo-5-membered heterocycle sulfides
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A highly efficient and simple route for the synthesis of benzo-5-membered heterocycles sulfides has been developed by the cross-coupling reaction of 2-mercaptobenzo-5-membered heterocycles with (hetero)arylaluminum reagents. Various benzo-5-membered heter
- Luo, Rui-Qiang,Guo, Shao Peng,Xiao, Hong-Liu,Li, Qing-Han
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- Lewis acid / Base-free Strategy for the Synthesis of 2-Arylthio and Selenyl Benzothiazole / Thiazole and Imidazole
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A Cu(II)-catalyzed Csp2-Se and Csp2-Sulfur bond formation was achieved with moderate to good yields without the aid of Lewis acid and base. The reaction is compatible with a wide range of heterocycles such as benzothiazole, thiazole, and imidazole. Also, this typical protocol is found to be active in thio-selenation via S-H activation. Additionally, we proposed a plausible mechanistic pathway involving Cu(III) putative intermediate.
- Balakishan, Guniganti,Kumaraswamy, Gullapalli,Narayanarao, Vykunthapu,Shankaraiah, Pagilla
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- Selective C-H chalcogenation of thiazoles: Via thiazol-2-yl-phosphonium salts
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Thiazoles and benzothiazoles undergo regioselective C2-H chalcogenation via the sequence of thiazole C2-functionalization with phosphines to produce phosphonium salts which in turn react with S- and Se-centered nucleophiles to give products of C2-H chalco
- Zi, You,Wagner, Konrad,Sch?mberg, Fritz,Vilotijevic, Ivan
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p. 5183 - 5191
(2020/07/23)
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- Palladium nanoparticles immobilized on a nano-silica triazine dendritic polymer: a recyclable and sustainable nanoreactor for C-S cross-coupling
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Dendrimers are of great interest due to their special structural topology and chemical versatility. Owing to their properties, dendrimers have found practical applications in catalytic processes as efficient nanoreactors. Therefore, we herein report an environmentally attractive strategy and highly efficient route for the synthesis of a wide variety of diaryl sulfides using palladium nanoparticles immobilized on a nano-silica triazine dendritic polymer (Pdnp-nSTDP) as a nanoreactor. In this manner, different diaryl or aryl heteroaryl sulfides and bis(aryl/heteroarylthio)benzene/anthracene/pyridine derivatives were preparedviaC-S cross-coupling reactions of aryl halides with diaryl/diheteroaryl disulfides under thermal conditions and microwave irradiation. The catalyst could be easily recovered and reused several times without any significant loss of its activity.
- Amiri Rudbari, Hadi,Landarani-Isfahani, Amir,Mirkhani, Valiollah,Moghadam, Majid,Mohammadpoor-Baltork, Iraj,Tangestaninejad, Shahram
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p. 21198 - 21205
(2020/06/26)
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- Room temperature nickel-catalyzed cross-coupling of aryl-boronic acids with thiophenols: Synthesis of diarylsulfides
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A NiCl2/2,2′-bipyridine-catalyzed cross-coupling of thiophenols with arylboronic acids has been developed for the synthesis of symmetric and unsymmetric diarylsulfides at room temperature and in air. This methodology is reliable and offers a mild and easy to operate process for the synthesis of arylthioethers, which are essential compounds with applications in the pharmaceutical and agricultural industries. This method avoids the use of expensive transition metals, such as Pd, Ir or Rh, sophisticated ligands and elevated temperatures. It also has a wide substrate scope (55 examples) and provides products in good to excellent yields (72-93%).
- Bhowmik, Amit,Fernandes, Rodney A.,Yadav, Mahesh
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p. 2447 - 2458
(2020/04/15)
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- HFIP Promoted Low-Temperature SNAr of Chloroheteroarenes Using Thiols and Amines
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A highly efficient and an unprecedented hexafluoro-2-propanol, promoting low-temperature aromatic nucleophilic substitutions of chloroheteroarenes, has been performed using thiols and (secondary) amines under base-free and metal-free conditions. The developed protocol also provides excellent regio-control for the selective functionalization of dichloroheteroarenes, while the utility of the protocol was demonstrated by the modification of a commercially available drug ceritinib.
- Bhujabal, Yuvraj B.,Vadagaonkar, Kamlesh S.,Gholap, Aniket,Sanghvi, Yogesh S.,Dandela, Rambabu,Kapdi, Anant R.
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p. 15343 - 15354
(2019/12/04)
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- Achieving Nickel Catalyzed C-S Cross-Coupling under Mild Conditions Using Metal-Ligand Cooperativity
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A simple and efficient approach of C-S cross-coupling of a wide variety of (hetero)aryl thiols and (hetero)aryl halides under mild conditions, mostly at room temperature, catalyzed by well-defined singlet diradical Ni(II) catalysts bearing redox noninnocent ligands is reported. Taking advantage of ligand centered redox events, the high-energetic Ni(0)/Ni(II) or Ni(I)/Ni(III) redox steps were avoided in the catalytic cycle. The cooperative participation of both nickel and the coordinated ligands during oxidative addition/reductive elimination steps allowed us to perform the catalytic reactions under mild conditions.
- Sikari, Rina,Sinha, Suman,Das, Siuli,Saha, Anannya,Chakraborty, Gargi,Mondal, Rakesh,Paul, Nanda D.
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p. 4072 - 4085
(2019/04/01)
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- Generation of Aryl Radicals from Aryl Halides: Rongalite-Promoted Transition-Metal-Free Arylation
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A new and practical method for the generation of aryl radicals from aryl halides is reported. Rongalite as a novel precursor of super electron donors was used to initiate a series of electron-catalyzed reactions under mild conditions. These transition-metal-free radical chain reactions enable the efficient formation of C-C, C-S, and C-P bonds through homolytic aromatic substitution or SRN1 reactions. Moreover, the synthesis of antipsychotic drug Quetiapine was performed on gram scale through the described method. This protocol demonstrated its potential as a promising arylation method in organic synthesis.
- Yu, Fazhi,Mao, Runyu,Yu, Mingcheng,Gu, Xianfeng,Wang, Yonghui
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p. 9946 - 9956
(2019/09/04)
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- Method for synthesizing asymmetric sulfide from molecular oxygen oxidation water phase under catalysis of water-soluble transition metal compound
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Aiming at problems that in the prior art organic solvent pollution can be caused and a great number of reaction byproducts are generated when asymmetric sulfides are prepared, the invention disclosesa method for synthesizing an asymmetric sulfide from a molecular oxygen oxidation water phase under catalysis of a water-soluble transition metal compound. The method comprises the following steps: dispersing a sulfydryl compound and a hydrazine compound as substrates in a mole ratio of 1:1 into an alkali solution, and at 40-100 DEG C, in the presence of oxygen, and with a water-soluble transitionmetal compound as a catalyst, stirring to carry out reactions, thereby obtaining the asymmetric sulfide. By adopting the method, molecular oxygen is adopted as an oxidant, and water is adopted as a solvent, so that an organic solvent is avoided, a high yield can be achieved, and the problem of byproducts can be generally avoided.
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Paragraph 0081-0084
(2019/07/29)
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- Surfactant-Type Catalyst for Aerobic Oxidative Coupling of Hydrazine with Thiol in Water
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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)
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- Chemoselective Chan-Lam Coupling Reactions between Benzimidazoline-2-thiones and Arylboronic Acids
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An efficient Chan-Lam-type methodology for the selective synthesis of S-arylbenzimidazoles and N,S-diarylbenzimidazoles was developed. The selectivity was controlled by varying the amount of the catalyst Cu(OAc)2·H2O, temperature, an
- Liu, Xing,Dong, Zhi-Bing
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p. 11524 - 11532
(2019/10/02)
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- Ligand-Free CuI-Catalyzed Chemoselective S-Arylation of 2-Mercaptobenzimidazole with Aryl Iodides
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A practical and efficient strategy for the chemoselective C-S cross-coupling of 2-mercaptobenzimidazole derivatives with a range of substituted aryl iodides is described. Under the optimized conditions of 5 mol% CuI and 100 °C, a variety of S-arylated products were obtained in good to excellent yields (up to 92 %) without the need for assisting ligands.
- Tan, Bryan Yong-Hao,Teo, Yong-Chua
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supporting information
p. 2056 - 2060
(2018/09/18)
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- Copper(I)-Catalyzed Tandem One-Pot Synthesis of 2-Arylthiobenzothiazoles and 2-Arylthiobenzoxazoles in Water
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An efficient tandem process for the preparation of 2-arylthiobenzothiazoles has been developed. By condensation of 2-aminobenzenethiol with tetramethylthiuram disulfide (TMTD), 2-mercaptobenzothiazoles was in situ generated, which susequently underwent coupling with iodobenzenes to give the desired 2-arylthiobenzothiazoles fluently in a one-pot manner. This method can also be used for the synthesis of 2-arylthiobenzoxazoles. Inexpensive metal catalyst and ligand, mild reaction temperature, and water as solvent make this protocol practically valuable and useful in organic synthesis.
- Liu, Xing,Zhang, Shi-Bo,Zhu, Hui,Dong, Zhi-Bing
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p. 11703 - 11711
(2018/10/02)
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- Visible-Light-Mediated Synthesis of Unsymmetrical Diaryl Sulfides via Oxidative Coupling of Arylhydrazine with Thiol
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A metal-free visible-light-promoted oxidative coupling between thiols and arylhydrazines has been developed to afford diaryl sulfides using a catalytic amount of rose bengal as photocatalyst under aerobic conditions. A library of unsymmetrical diaryl sulfides with broad functionalities was synthesized in good yields at room temperature. The present methodology is also applicable to benzo[d]thiazole-2-thiols, benzo[d]oxazole-2-thiol, 1H-benzo[d]imidazole-2-thiols, and 1H-imidazole-2-thiol.
- Kibriya, Golam,Mondal, Susmita,Hajra, Alakananda
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supporting information
p. 7740 - 7743
(2018/12/14)
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- Facile synthesis of S-arylisothioureas via the S-arylation of arylthioureas with aryl iodides in water
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An environmentally benign, simple and highly efficient protocol for the synthesis of S-arylisothiourea derivatives has been achieved in good to excellent yields by reacting a series of aryl iodides with arylthioureas, using inexpensive CuSO4·5H2O as catalyst in water without PTC (phase transfer catalyst). The protocol features easy performance, good to excellent yields, good tolerance towards a variety of functional groups, which could be useful for the preparation of some biologically active compounds.
- Liu, Xing,Zhu, Hui,Zhang, Shi-Bo,Cheng, Yu,Peng, Han-Ying,Dong, Zhi-Bing
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supporting information
p. 3165 - 3170
(2018/07/13)
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- Copper-Catalyzed One-Pot Synthesis of Chalcogen-Benzothiazoles/Imidazo[1,2- a ]pyridines with Sulfur/Selenium Powder and Aryl Boronic Acids
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An efficient and convenient copper-catalyzed oxidative chalcogenation of benzothiazoles and imidazo[1,2- a ]pyridines with sulfur/selenium powder and aryl boronic acids was developed. This procedure allows access to a wide range of structurally diverse arylchalcogen-substituted benzothiazoles/imidazo[1,2- a ]pyridines in good yields and with good functional group tolerance. A biological evaluation revealed that some of the obtained products exhibited in vitro antiproliferative activities on human-derived lung, stomach, esophageal, and breast cancer cell lines.
- Guo, Tao,Wei, Xu-Ning,Zhu, Ying-Li,Chen, Huan,Han, Shu-Lei,Ma, Yong-Cheng
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p. 1530 - 1536
(2018/05/25)
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- Photo-induced copper-catalyzed C-H chalcogenation of azoles at room temperature
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Inexpensive copper catalysts enabled direct C-H chalcogenations at ambient temperature by means of photo-induced catalysis. The expedient copper catalysis set the stage for C-S and C-Se bond formation from readily accessible non-volatile elemental chalcogens. The photo-assisted copper catalysis manifold proved suitable for a wide range of substrates with good functional group tolerance and exhibited high catalytic efficacy even at a reaction temperature of 25 °C.
- Gandeepan, Parthasarathy,Mo, Jiayu,Ackermann, Lutz
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supporting information
p. 5906 - 5909
(2017/07/11)
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- Pd-PVP-Fe (palladium-poly(N-vinylpyrrolidone)-iron) catalyzed S-arylation of thiols with aryl halides in aqueous media
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Pd-PVP-Fe (palladium-poly(N-vinylpyrrolidone)-iron) nano catalyst catalyzes selective C–S cross-coupling (S-arylation) reactions of thiols with aryl halides and avoids the formation of S–S (disulfide) homocoupling byproducts. The reactions were carried out in aqueous media using only 0.23?mol% palladium with high selectivity and short reaction time. The effects of the Pd0and Fe0moieties on the C–S cross-coupling reaction mechanism, yield, and selectivity were investigated. The yield and selectivity can be controlled by adjusting the order of adding the reactants and catalyst into the reaction medium. The X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), electron backscatter diffraction (EBSD) microscopy, energy dispersive X-ray (EDX) spectroscopy, and thermal gravimetric analysis (TGA) tools were used to characterize the catalyst. The C–S cross-coupling reaction process could be repeated up to six times without losing effectiveness. The metals leaching of Pd-PVP-Fe nanocatalyst after reusing cycles were investigated by atomic absorption spectroscopic (AAS) and EDX spectroscopy. The nature of Pd metal after the first run of the C–S cross-coupling reaction was studied by UV–vis spectrophotometry. The morphology of bimetallic nanocatalyst after the first run of the C–S cross-coupling reaction was investigated by SEM, EBSD, and EDX microscopy.
- Ghaderi-Shekhi Abadi, Parvaneh,Rafiee, Ezzat,Joshaghani, Mohammad
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p. 162 - 170
(2016/07/25)
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- Efficient synthesis of unsymmetrical heteroaryl thioethers and chalcogenides by alkali hydroxide-mediated SNAr reactions of heteroaryl halides and dichalcogenides
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An efficient alkali hydroxide-mediated SNAr reaction of heteroaryl halides has been developed for the practical synthesis of the useful unsymmetrical heteroaryl thioethers and chalcogenides. The usually odorless, easily available, lowly toxic, and easily stored and handled diorganyl dichalcogenides can be used as safer and convenient chalcogen nucleophile precursors and diverse unsymmetrical heteroaryl chalcogenides can be obtained in good to high yields by the method.
- Ma, Xiantao,Liu, Quan,Jia, Xiaojuan,Su, Chenliang,Xu, Qing
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p. 56930 - 56935
(2016/07/06)
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- Regioselective, Solvent- and Metal-Free Chalcogenation of Imidazo[1,2-a]pyridines by Employing I2/DMSO as the Catalytic Oxidation System
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Highly efficient molecular-iodine-catalyzed chalcogenations (S and Se) of imidazo[1,2-a]pyridines were achieved by using diorganoyl dichalcogenides under solvent-free conditions. This approach afforded the desired products that had been chalcogenated regioselectively at the C3 position in up to 96 % yield by using DMSO as an oxidant, in the absence of a metal catalyst, and under an inert atmosphere. This mild, green approach allowed the preparation of different types of chalcogenated imidazo[1,2-a]pyridines with structural diversity. Furthermore, the current protocol was also extended to other N-heterocyclic cores.
- Rafique, Jamal,Saba, Sumbal,Rosário, Alisson R.,Braga, Antonio L.
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supporting information
p. 11854 - 11862
(2016/08/05)
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- New Synthesis and Biological Evaluation of Benzothiazole Derivates as Antifungal Agents
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In search of new antifungal agrochemicals that could replace commercially available, aryl-2-mercaptobenzothiazoles were synthesized. They were prepared by two methodologies, using both photostimulated reaction and microwave assisted reaction. These reactions took place without the use of metallic catalyst by a one-pot procedure with excellent yields (70-98%). Synthesized compounds were evaluated for fungal growth inhibition against Botrytis cinerea. Most of the compounds have an excellent antifungal activity, and three of these showed a superior inhibitory effect to commercial fungicide Triadimefon. IC50 values observed for 2-(phenylthio)benzothiazole, 2-(2-chlorophenylthio)benzothiazole, and 2-(3-chlorophenyl thio)benzothiazole were 0.75, 0.69, and 0.65 μg mL-1, respectively.
- Cano, Natividad Herrera,Ballari, María S.,López, Abel G.,Santiago, Ana N.
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p. 3681 - 3686
(2015/04/27)
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- AROMATIC SULFIDE COMPOUNDS AND METHODS AND USE THEREOF
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Described herein, inter alia, are aromatic sulfide compositions and methods for treating or preventing cancer using the same.
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Page/Page column 0168; 0179
(2015/11/03)
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- Palladium Nanoparticles Immobilized on Nanosilica Triazine Dendritic Polymer (Pd np -nSTDP) as Catalyst in the Synthesis of Mono-, Di-, and Trisulfides through C-S Cross-Coupling Reactions
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A wide variety of diaryl sulfides has been synthesized in excellent yields via C-S cross-couplings of aryl/heteroaryl halides with aromatic/heteroaromatic thiols in the presence of palladium nanoparticles immobilized on nanosilica triazine dendritic polymer (Pd np -nSTDP) as a reusable catalyst under thermal conditions and microwave irradiation. Pd np -nSTDP also showed excellent catalytic activity for the preparation of a series of di- and trisulfides with benzene, pyridine, pyrimidine, and/or 1,3,5-triazine as the central cores by one-pot multi C-S cross-coupling reactions. Georg Thieme Verlag Stuttgart. New York.
- Isfahani, Amir Landarani,Mohammadpoor-Baltork, Iraj,Mirkhani, Valiollah,Moghadam, Majid,Khosropour, Ahmad Reza,Tangestaninejad, Shahram,Nasr-Esfahani, Mahboobeh,Rudbari, Hadi Amiri
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supporting information
p. 645 - 652
(2014/04/03)
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- Novel copper/PEG-400 catalyst systems for chemoselective S- and N-arylation of 2-mercaptobenzothiazole
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A novel approach for chemoselective S- and N-arylation of 2-mercaptobenzothiazole was developed by copper/PEG-400 catalyst systems. Copper source and reaction temperature play an important role in this protocol, selective S-arylation of 2-mercaptobenzothiazole was achieved by using CuI/PEG-400/50 °C catalyst system, while selective N-arylation was achieved with CuO/PEG-400/140 °C catalyst system. Both are compatible with a variety of aryl halides and selectively give the desired S- and N-arylation products in good to excellent yields, respectively.
- Li, Xiaokang,Yuan, Tangjun,Yang, Yu,Chen, Junmin
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supporting information
p. 9652 - 9660
(2015/01/09)
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- Synthesis of heteroaryl containing sulfides via enaminone ligand assisted, copper-catalyzed C-S coupling reactions of heteroaryl thiols and aryl halides
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The C-S cross coupling reactions between electron deficient heteroaryl thiols and aryl halides have been smoothly performed to provide various heteroaryl containing sulfides in the presence of copper catalyst and enaminone ligand. the Partner Organisations 2014.
- Liu, Yunyun,Huang, Bin,Cao, Xiaoji,Wu, Dan,Wan, Jie-Ping
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p. 37733 - 37737
(2014/11/07)
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- Sulfur-silicon bond activation catalysed by Cl/Br ions: Waste-free synthesis of unsymmetrical thioethers by replacing fluoride catalysis and fluorinated substrates in SNAr reactions
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In contrast to conventional activation of Nu-SiR3 reagents by F ion attributed to the strong affinity of Si to F, S-Si activation can now be achieved using Cl/Br ions of TBAX as catalysts via formation of weaker X-Si bonds and Me3Si-X. This led to a waste-free synthesis of unsymmetrical thioethers via F-free SNAr reactions of activated (hetero)aryl halides and RS-SiMe3, with recovery of the useful Me3Si-X reagent in high yields. This journal is the Partner Organisations 2014.
- Jia, Xiaojuan,Yu, Lei,Liu, Jianping,Xu, Qing,Sickert, Marcel,Chen, Lianhui,Lautens, Mark
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supporting information
p. 3444 - 3449
(2014/07/08)
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- Diaryl and heteroaryl sulfides: Synthesis via sulfenyl chlorides and evaluation as selective anti-breast-cancer agents
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A mild protocol for the synthesis of diaryl and heteroaryl sulfides is described. In a one-pot procedure, thiols are converted to sulfenyl chlorides and reacted with arylzinc reagents. This method tolerates functional groups including aryl fluorides and chlorides, ketones, as well as N-heterocycles including pyrimidines, imidazoles, tetrazoles, and oxadiazoles. Two compounds synthesized by this method exhibited selective activity against the MCF-7 breast cancer cell line in the micromolar range.
- Yonova, Ivelina M.,Osborne, Charlotte A.,Morrissette, Naomi S.,Jarvo, Elizabeth R.
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p. 1947 - 1953
(2014/04/03)
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- Synthesis of 2- N / S / C -substituted benzothiazoles via intramolecular cyclative cleavage of benzotriazole ring
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The synthesis of numerous 2-N/S/C-substituted benzothiazoles was achieved from substituted thiocarbonylbenzotriazoles via free-radical intramolecular cyclative cleavage of the benzotriazole ring in the presence of (TMS) 3SiH and AIBN under mild
- Kumar, Dhananjay,Mishra, Bhuwan B.,Tiwari, Vinod K.
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p. 251 - 266
(2014/01/17)
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- Substrate-promoted ligand-free CuI catalyzed S-arylation of 2-mercaptobenzothiazoles with aryl iodides in water
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A green and efficient method has been developed for the cross-coupling of 2-mercaptobenzothiazoles with aryl iodides in water. The reactions proceeded smoothly under ligand-free conditions in the presence of TBAB to give the corresponding products in good yields. The protocol showed good tolerance toward a variety of functional groups. A substrate-promoted mechanism for this catalytic reaction has been proposed.
- He, Guozhen,Huang, Yuan,Tong, Yao,Zhang, Jie,Zhao, Dan,Zhou, Shuangli,Han, Shiqing
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supporting information
p. 5318 - 5321
(2013/09/12)
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- N-heterocyclic carbene copper(I) complex-catalyzed direct C-H thiolation of benzothiazoles
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N-heterocyclic carbene (NHC) copper(I) complexes based on imidazol-2-ylidene and 1,2,3-triazol-5-ylidene catalyzed the direct C-H thiolation of benzothiazoles and benzoxazoles with aryl and alkyl thiols to give 2-aryl and 2-alkylthiobenzothiazoles in moderate-to-good yields. The NHC copper(I) complex [(IPr)CuI] was the most effective catalyst for the reaction among the NHC-Cu(I) complexes examined in this study.
- Inomata, Hiroshi,Toh, Ayumi,Mitsui, Takashi,Fukuzawa, Shin-Ichi
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supporting information
p. 4729 - 4731
(2013/08/23)
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- Copper oxide nanoparticle-catalyzed chalcogenation of the carbon-hydrogen bond in thiazoles: Synthesis of 2-(organochalcogen) thiazoles
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We present (homepage: www.ufsm.br) herein the application of copper nanoparticles/dio-rganyl dichalcogenides to promote the synthesis of 2-(organochalcogen)thiazoles via direct carbon-hydro-gen bond activation in thiazoles. A systematic study of the catalytic system revealed that the presence and amount of base played an essential role in this reaction. The results revealed that electron-donating and electron-withdrawing substituents, in the aromat-ic ring bonded to the chalcogen atom of diorganyl di-chalcogenides, required one equiv. of base, while when neutral substituents were present two equiv. of base were needed to deliver the products in similar yields.
- Rosario, Alisson R.,Casola, Kamila K.,Oliveira, Carla E.S.,Zeni, Gilson
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supporting information
p. 2960 - 2966
(2014/03/21)
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- Copper-catalyzed direct thiolation of xanthines and related heterocycles with disulfides
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A novel copper-catalyzed, base-free direct thiolation of xanthines and related heterocycles is described, featuring the use of inexpensive Cu(OAc) 2·H2O as the catalyst, O2 as a clean and cheap oxidant, and easy-to-handle
- He, Zuying,Luo, Fang,Li, Yinglong,Zhu, Gangguo
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supporting information
p. 5907 - 5910
(2013/10/21)
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- Bio-based green solvent mediated disulfide synthesis via thiol couplings free of catalyst and additive
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The bio-based green solvent ethyl lactate has been found to be a particularly efficient medium for oxidative coupling reactions of thiols yielding a broad array of disulfides. As a green solvent, ethyl lactate has shown an interesting promotion effect on the transformation by mediating corresponding reactions with high efficiency without using any catalyst or additive. The Royal Society of Chemistry 2013.
- Liu, Yunyun,Wang, Hang,Wang, Chunping,Wan, Jie-Ping,Wen, Chengping
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p. 21369 - 21372
(2013/11/06)
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- Heterogeneous magnetic catalyst for S-arylation reactions
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A convenient method for the synthesis of monodisperse, superparamagnetic copper ferrite (CuFe2O4) nanoparticles with high surface area has been described. The synthesized material was characterized by various techniques. XRD showed the nanocrystalline nature of CuFe2O 4 with a crystallite size of 6 nm. TEM analysis showed that uniform spherical CuFe2O4 particles are formed with a size of 55 ± 5 nm. N2 adsorption/desorption measurements confirmed the mesoporous nature of the sample with surface area >216 m2 g -1. The field dependent magnetization, illustrated by VSM and saturation magnetization was found to be 44 emu g-1. The catalytic applications of the synthesized CuFe2O4 nanoparticles were explored for the cross-coupling of thiols with diverse range of aryl halides. Aryl iodides and bromides result in biarylsulfides in good to excellent yields (62-98%) whereas aryl chlorides gave significant amount of diaryldisulfide. Scope of this catalytic protocol further extended to one-pot synthesis of biologically important tricyclic dibenzothiazepines. The superparamagnetic nature of CuFe2O4 nanoparticles was found to be advantageous for their easy, quick and quantitative separation from the reaction mixture. Negligible leaching of Cu and Fe in consecutive cycles makes the catalyst economical and environmentally benign.
- Panda, Niranjan,Jena, Ashis Kumar,Mohapatra, Sasmita
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experimental part
p. 258 - 264
(2012/08/28)
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- Efficient recyclable CuI-nanoparticle-catalyzed S-arylation of thiols with aryl halides on water under mild conditions
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CuI nanoparticles efficiently catalyzed the C-S cross coupling of aryl and alkyl thiols with aryl halides in the absence of ligands on water under mild conditions. A wide range of diaryl sulfides and aryl alkyl sulfides are synthesized in good to excellent yields utilizing this protocol. This procedure is particularly noteworthy given its mild conditions, avoiding the undesired formation of disulfides through oxidation of thiols. The recovery and successful reutilization of the catalyst is described. Furthermore, the directed synthesis of bisarylated product is presented. The Royal Society of Chemistry 2012.
- Xu, Hua-Jian,Liang, Yu-Feng,Zhou, Xin-Feng,Feng, Yi-Si
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supporting information; experimental part
p. 2562 - 2568
(2012/04/23)
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- Synthesis of aryl thioethers through the N -chlorosuccinimide-promoted cross-coupling reaction of thiols with Grignard reagents
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A convenient one-pot approach for the synthesis of aryl sulfides through the coupling of thiols with Grignard reagents in the presence of N-chlorosuccinimide is described. The sulfenylchlorides were formed when thiols were treated with N-chlorosuccinimide, and the resulting sulfenylchlorides were then directly reacted with Grignard reagents to provide aryl sulfides in good to excellent yields under mild reaction conditions. Functional groups including ester, fluoro, and chloro are tolerated by the reaction conditions employed. It is important to note that this method has a short reaction time (30 min in total) and represents an alternative approach for the synthesis of aryl sulfides over the existing protocols.
- Cheng, Jun-Hao,Ramesh, Chintakunta,Kao, Hsin-Lun,Wang, Yu-Jen,Chan, Chien-Ching,Lee, Chin-Fa
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p. 10369 - 10374
(2013/01/15)
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- Chan-lam-type s-arylation of thiols with boronic acids at room temperature
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In this work, an efficient CuSO4-catalyzed S-arylation of thiols with aryl and heteroaryl boronic acids at room temperature is established. This catalytic system can tolerate a wide variety of thiols and arylboronic acids in the presence of only 5 mol % of CuSO4 as the catalyst and inexpensive 1,10-phen?H2O as the ligand. Moreover, this catalytic system used environment-friendly solvent (EtOH) and oxidant (oxygen).
- Xu, Hua-Jian,Zhao, Yong-Qiang,Feng, Teng,Feng, Yi-Si
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experimental part
p. 2878 - 2884
(2012/05/04)
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- Lewis acid-catalyzed, copper(II)-mediated synthesis of heteroaryl thioethers under base-free conditions
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A Lewis acid (AgI, NiII, or FeII) catalyzed, CuII-mediated thiolation reaction between heteroarenes and thiols was achieved with good yield under base-free conditions. DMSO could serve as an effective methylthiolation reagent for the synthesis of heterocyclic methyl thioethers.
- Dai, Chao,Xu, Zhaoqing,Huang, Fei,Yu, Zhengkun,Gao, Yan-Feng
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experimental part
p. 4414 - 4419
(2012/06/18)
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- Efficient copper-catalyzed C-S cross-coupling of heterocyclic thiols with aryl iodides
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A copper-catalyzed cross-coupling of heterocyclic thiols with aryl iodides is reported. The reaction was carried out in the presence of CuI (5 mol %), 1,10-phenanthroline (10 mol %) and K2CO3 (1.3 equiv) in DMF at 120 °C. A variety o
- Niu, Liang-Feng,Cai, Yan,Liang, Chao,Hui, Xin-Ping,Xu, Peng-Fei
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supporting information; experimental part
p. 2878 - 2881
(2011/05/13)
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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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- Copper-mediated C-H activation/C-S cross-coupling of heterocycles with thiols
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We report the synthesis of a series of aryl- or alkyl-substituted 2-mercaptobenzothiazoles by direct thiolation of benzothiazoles with aryl or alkyl thiols via copper-mediated aerobic C-H bond activation in the presence of stoichiometric CuI, 2,2′-bipyridine and Na2CO3. We also show that the approach can be extended to thiazole, benzimidazole, and indole substrates. In addition, we present detailed mechanistic investigations on the Cu(I)-mediated direct thiolation reactions. Both computational studies and experimental results reveal that the copper-thiolate complex [(L)Cu(SR)] (L: nitrogen-based bidentate ligand such as 2,2′-bipyridine; R: aryl or alkyl group) is the first reactive intermediate responsible for the observed organic transformation. Furthermore, our computational studies suggest a stepwise reaction mechanism based on a hydrogen atom abstraction pathway, which is more energetically feasible than many other possible pathways including β-hydride elimination, single electron transfer, hydrogen atom transfer, oxidative addition/reductive elimination, and σ-bond metathesis.
- Ranjit, Sadananda,Lee, Richmond,Heryadi, Dodi,Shen, Chao,Wu, Ji'En,Zhang, Pengfei,Huang, Kuo-Wei,Liu, Xiaogang
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scheme or table
p. 8999 - 9007
(2011/12/03)
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- Copper-catalyzed direct thiolation of azoles with aliphatic thiols
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Cu(ii)-catalyzed direct thiolation of azoles with thiols is described via intermolecular C-S bond formation/C-H functionalization under oxidative conditions. Both aryl thiols and aliphatic thiols are used as coupling partners, and furnished the thiolation
- Zhou, An-Xi,Liu, Xue-Yuan,Yang, Ke,Zhao, Shu-Chun,Liang, Yong-Min
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supporting information; scheme or table
p. 5456 - 5462
(2011/08/07)
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- Synthesis of 2-thio-substituted benzothiazoles via a domino condensation/S -arylation/heterocyclization process
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Condensation of carbon disulfide with thiols in the presence of K 2CO3 generates carbonotrithioate salts in situ, which undergo coupling with 2-iodoanilines and subsequent intramolecular condensation and elimination under assistance of CuBr to afford 2-thio-substituted benzothiazoles. Both aliphatic and aromatic thiols are compatible with this process, delivering the corresponding heterocycles with good diversity.
- Shi, Liu,Liu, Xiangqian,Zhang, Hui,Jiang, Yongwen,Ma, Dawei
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experimental part
p. 4200 - 4204
(2011/07/31)
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- Rhodium-catalyzed phenylthiolation reaction of heteroaromatic compounds using α-(phenylthio)isobutyrophenone
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In the presence of catalytic amounts of RhH(PPh3)4 and 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-benzothiazoles, 1,3-benzoxazoles, and benzothiophene reacted with α-(phenylthio) isobutyrophenone giving 2-phenylthio derivatives. Reactive monocyclic heteroaromatics, 1-methyl-1,2,3,4-tetrazole and 2-cyanothiophene were also converted into the 5-phenylthio derivatives. The use of an appropriate phenylthio transfer reagent is crucial for the efficient catalyzed conversion of heteroaromatic C-H bonds into C-S bonds.
- Arisawa, Mieko,Toriyama, Fumihiko,Yamaguchi, Masahiko
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p. 2344 - 2347
(2011/05/16)
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- Efficient ligand-free copper-catalyzed C-S cross-coupling of thiols with aryl iodides using KF/Al2O3 as base
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We report a mild, convenient, environmentally friendly, and ligand-free synthetic protocol for the cross-coupling reaction of aryl iodides and thiols using 10 mol % CuI with KF/Al2O3 as the base, in DMF at 110 °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.
- Feng, Yi-Si,Li, Yuan-Yuan,Tang, Lin,Wu, Wei,Xu, Hua-Jian
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experimental part
p. 2489 - 2492
(2010/06/14)
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- Ring opening of pymisyl-protected aziridines with organocuprates
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The pyrimidine-2-sulfonyl (pymisyl) group is introduced as a new protecting group that can be used to activate aziridines towards ring opening. It is readily introduced and removed under mild conditions. Regioselective ring opening of pymisyl-protected 2-methyl-aziridine with organocuprates gives the corresponding sulfonamides in high yields, and the pymisyl group can subsequently be removed upon treatment with a thiolate. The versatility of this new nitrogen protecting group is illustrated with a new synthesis of Selegiline, a monoamine oxidase-B inhibitor marketed for the treatment of Parkinson's disease. Easy on'easy off: The pymisyl group is introduced as a new protecting group for the activation of aziridines towards ring opening with organocuprates (see scheme). It is readily removed under very mild conditions with thiolates. The versatility of the approach is illustrated in a new synthesis of Selegiline, a drug marketed for the treatment of Parkinson's disease.
- Bornholdt, Jan,Felding, Jakob,Clausen, Rasmus P.,Kristensen, Jesper L.
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supporting information; experimental part
p. 12474 - 12480
(2010/12/25)
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- A reusable FeCl3·6H2O/cationic 2,2′-bipyridyl catalytic system for the coupling of aryl iodides with thiols in water under aerobic conditions
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In this study, an FeCl3·6H2O/cationic 2,2′-bipyridyl system was employed as a catalyst in the coupling of aryl iodides with thiols to form an aryl-sulfur bond in refluxed water under aerobic conditions. The residual aqueous solution after extraction could be reused for several cycles without a significant decrease in activity.
- Wu, Wei-Yi,Wang, Jui-Chan,Tsai, Fu-Yu
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experimental part
p. 326 - 329
(2010/04/22)
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- Copper(I)-catalyzed cascade synthesis of 2-substituted 1,3-benzothiazoles: Direct access to benzothiazolones
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An efficient cascade process for the preparation of 2-substituted 1,3-benzothiazoles directly from 2-haloaryl isothiocyanates and O or S nucleophiles by a Cu-catalyzed, intramolecular, C-S bond formation has been developed. This cascade method is viable f
- Murru, Siva,Mondal, Pravat,Yella, Ramesh,Patel, Bhisma K.
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experimental part
p. 5406 - 5413
(2010/02/28)
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