22865-50-5Relevant academic research and scientific papers
CuMoO4 Bimetallic Nanoparticles, An Efficient Catalyst for Room Temperature C?S Cross-Coupling of Thiols and Haloarenes
Panigrahi, Reba,Sahu, Santosh Kumar,Behera, Pradyota Kumar,Panda, Subhalaxmi,Rout, Laxmidhar
, p. 620 - 624 (2019/12/27)
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.
Bimetallic BaMoO4 nanoparticles for the C-S cross-coupling of thiols with haloarenes
Panda, Subhalaxmi,Sahu, Santosh Kumar,Behera, Pradyota Kumar,Panigrahi, Reba,Garnaik, Bamakanta,Rout, Laxmidhar
supporting information, p. 2500 - 2504 (2020/02/20)
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.
Pd (II) immobilized on clinoptilolite as a highly active heterogeneous catalyst for ullmann coupling-type s-arylation of thiols with aryl halides
Alizadeh, Abdollah,Khalilzadeh, Mohammad A.,Alipour, Eskandar,Zareyee, Daryoush
, p. 657 - 666 (2020/08/24)
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.
Highly active mesoionic chalcogenone zinc(II) derivatives for C-S cross-coupling reactions
Vaddamanu, Moulali,Prabusankar, Ganesan,Velappan, Kavitha
, p. 129 - 140 (2019/12/26)
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.
Homoleptic and heteroleptic Zn(ii) selone catalysts for thioetherification of aryl halides without scrubbing oxygen
Vaddamanu, Moulali,Velappan, Kavitha,Prabusankar, Ganesan
, p. 3574 - 3583 (2020/03/17)
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.
CuI-catalyzed direct synthesis of diaryl thioethers from aryl boronic acids and arylsulfonyl chlorides
Huang, Keke,Yang, Min,Lai, Xiao-Jing,Hu, Xin,Qiu, Guanyinsheng,Liu, Jin-Biao
, (2019/12/27)
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.
Surfactant-Type Catalyst for Aerobic Oxidative Coupling of Hydrazine with Thiol in Water
Ren, Xuanhe,Tang, Shanyu,Li, Longjia,Li, Jiao,Liang, Helong,Li, Ganzhong,Yang, Guanyu,Li, Heng,Yuan, Bingxin
, p. 8683 - 8690 (2019/07/08)
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.
Cerium catalyst promoted C-S cross-coupling: Synthesis of thioethers, dapsone and RN-18 precursors
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)
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.
An efficient protocol for the synthesis of thioethers via iron-catalyzed cross-coupling reaction and its mechanistic investigation
Sindhu,Abi,Mathai, George,Anilkumar, Gopinathan
, p. 270 - 276 (2018/11/26)
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).
C-S coupling with nitro group as leaving group via simple inorganic salt catalysis
Xuan, Maojie,Lu, Chunlei,Lin, Bo-Lin
supporting information, (2019/08/26)
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.
