- Rearrangement of alkynyl sulfoxides catalyzed by gold(I) complexes
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A series of gold(I)-catalyzed rearrangement reactions of alkynyl sulfoxides are reported. Homopropargylsulfoxides are rearranged to benzothiepinones or benzothiopines, while α-thioenones are formed in the reaction of propargylsulfoxides. The proposed mech
- Shapiro, Nathan D.,Toste, F. Dean
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- Chromoselective Synthesis of Sulfonyl Chlorides and Sulfonamides with Potassium Poly(heptazine imide) Photocatalyst
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Among external stimuli used to promote a chemical reaction, photocatalysis possesses a unique one—light. Photons are traceless reagents that provide an exclusive opportunity to alter chemoselectivity of the photocatalytic reaction varying the color of incident light. This strategy may be implemented by using a sensitizer capable to activate a specific reaction pathway depending on the excitation light. Herein, we use potassium poly(heptazine imide) (K-PHI), a type of carbon nitride, to generate selectively three different products from S-arylthioacetates simply varying the excitation light and otherwise identical conditions. Namely, arylchlorides are produced under UV/purple, sulfonyl chlorides with blue/white, and diaryldisulfides at green to red light. A combination of the negatively charged polyanion, highly positive potential of the valence band, presence of intraband states, ability to sensitize singlet oxygen, and multi-electron transfer is shown to enable this chromoselective conversion of thioacetates.
- Antonietti, Markus,Guldi, Dirk M.,Markushyna, Yevheniia,Savateev, Aleksandr,Schü?lbauer, Christoph M.,Ullrich, Tobias
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supporting information
p. 20543 - 20550
(2021/08/12)
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- Transformation of arylboronic acids with sodium thiosulfate into organodisulfides catalyzed by a recyclable polyoxometalate-based Cr(iii) catalyst
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Organo disulfides represent an abundant class of compounds in chemical biology, pharmaceutical fields, and industry. They are traditionally synthesized by the oxidation of mercaptan in the presence of an organic ligand supported metal catalyst or toxic oxidants under harsh conditions. Here, we disclose a highly-efficient pathway in which disulfide is synthesized by organic boric acid and Na2S2O3 using the catalyst (NH4)3[CrMo6O18(OH)6], demonstrating a high activity and excellent selectivity. Various boric acid derivatives have been successfully transformed into the corresponding disulfides. Mechanistic insights have been furnished based on the observation of intermediate and control experiments.
- Chang, Yalin,Li, Huiyi,Tao, Chaofu,Wang, Aiping,Wei, Yongge,Xie, Ya,Yu, Han,Yu, Shunming
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supporting information
p. 6059 - 6064
(2021/08/23)
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- Practical and efficient recyclable oxidative system for the preparation of symmetrical disulfides under aerobic conditions
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An efficient and practical oxidative coupling of thiols to symmetrical disulfides is developed at room temperature under aerobic conditions. The commercially available sodium methoxide solution 30 wt. % in methanol together with the air was used as a retrievable promoter system and green oxidant, respectively, for the preparation of symmetrical disulfides. The desired products were obtained in good to high yields by an economical procedure. No overoxidation of the symmetrical disulfides was observed, and various functional groups were well tolerated in the current protocol. Moreover, the new reagent reduces the generation of hazardous waste due to its high reusability. The reaction proceeded in the absence of light, and it was not inhibited by TEMPO. Also, the low yield of TEMPO-benzyl thiol adduct was detected under these conditions. Based on our experiments, a possible mechanism was proposed in the absence and presence of TEMPO.
- Ling, Ong Chiu,Heidelberg, Thorsten,Ching, Juan Joon,Khaligh, Nader Ghaffari
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p. 281 - 294
(2020/12/13)
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- Application of Bulky NHC-Rhodium Complexes in Efficient S-Si and S-S Bond Forming Reactions
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The efficient and straightforward syntheses of silylthioethers and disulfides are presented. The synthetic methodologies are based on new rhodium complexes containing bulky N-heterocyclic carbene (NHC) ligands that turned out to be efficient catalysts in thiol and thiol-silane coupling reactions. These green protocols, which use easily accessible reagents, allow obtaining compounds containing S-Si and S-S bonds in solvent-free conditions. Additionally, preliminary tests on coupling of mono- and octahydro-substituted spherosilicates with selected thiols have proved to be very promising and showed that these catalytic systems can be used for the synthesis of a novel class of functionalized silsesquioxane derivatives.
- Bo?t, Ma?gorzata,?ak, Patrycja
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supporting information
p. 17579 - 17585
(2021/11/18)
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- Green Aerobic Oxidation of Thiols to Disulfides by Flavin-Iodine Coupled Organocatalysis
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Coupled catalysis using a riboflavin-derived organocatalyst and molecular iodine successfully promoted the aerobic oxidation of thiols to disulfides under metal-free mild conditions. The activation of molecular oxygen occurred smoothly at room temperature through the transfer of electrons from the iodine catalyst to the biomimetic flavin catalyst, forming the basis for a green oxidative synthesis of disulfides from thiols.
- Iida, Hiroki,Kozako, Ryo,Oka, Marina
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supporting information
p. 1227 - 1230
(2021/06/21)
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- Cobalt catalysed aminocarbonylation of thiols in batch and flow for the preparation of amides
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The synthesis of amides from thiols through a cobalt-catalyzed aminocarbonylation is shown. After optimizing all the reaction parameters, the methodology makes possible the obtention of amides with variable yields, while competing reactions such as the formation of disulfides and ureas can be limited. The process works well with aromatic thiols with electron donating groups (EDG) whereas other thiols give reaction with lower yields. The previous process has been transferred and optimized into flow equipment, thus allowing using less CO in a safer way, and permitting the scaling up of the synthesis. Two drugs, moclobemide and itopride were prepared with this methodology, albeit only in the second case with good results. A mechanistic pathway is proposed.
- Domínguez, Gema,Ordu?a, Jose Maria,Pérez-Castells, Javier
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p. 30398 - 30406
(2021/10/20)
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- Substituted o-Aminophenols as Redox-Mediators in the Thiol Oxidation to Unsymmetrical Disulfides
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A number of substituted o-aminophenols has been investigated as redox mediators of the thiol oxidation to disulfides. The electrooxidation of o-aminophenols leads to the corresponding o-iminobenzoquinones. These compounds react with thiols in the solution with a formation of disulfides. It was established that the use of 4,6-di-tert-butyl-2-(tert-butylamino)phenol as a redox mediator can reduce the overpotential of the thiol oxidation by 0.2-1.4 V depending on the nature of the coupling thiols. The unsymmetrical disulfides with alkyl, aryl, and heteroaryl substituents were obtained as the result of the indirect electrosynthesis.
- Berberova, Nadezhda T.,Burmistrova, Daria A.,Galustyan, Andrey,Smolyaninov, Ivan V.
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- Multicomponent Synthesis of Sulfones and Sulfides from Triarylbismuthines and Sodium Metabisulfite in Deep Eutectic Solvents
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This study describes a novel and catalyst-free methodology for the multicomponent synthesis of a broad range of sulfones, disulfides, and sulfides from non-toxic triarylbismuthines (Ar3Bi) and sodium metabisulfite (Na2S2O5) in deep eutectic solvents (DESs). The fine tuning of the DESs properties allowed the solubility of all reagents, enhancing their reactivity, as well as, the recyclability of the reaction medium for at least 5 consecutive cycles. Thus, this versatile strategy uses non-toxic reagents without the need of metal catalysts in a sustainable solvent, being an interesting alternative to traditional hazardous protocols.
- Saavedra, Beatriz,Marset, Xavier,Guillena, Gabriela,Ramón, Diego J.
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supporting information
p. 3462 - 3467
(2020/06/04)
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- Synthetic method of diaryl disulfide compound
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The invention relates to a synthetic method of a diaryl disulfide compound. The method comprises the following steps of: in an organic solvent, under the condition of nitrogen, using arylboronic acidand sulfur as the reaction raw materials, carrying out free radical vulcanization/self-polymerization coupling reaction under the action of a transition metal silver catalyst to obtain the diaryl disulfide compound. The method is simple in reaction condition, simple and convenient in experimental operation and high in product yield and purity, opens up a synthetic route and method for preparationof the diaryl disulfide compound, and has good application potential and research value.
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Paragraph 0066-0075
(2020/11/23)
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- Preparation method of diphenyl disulfide compounds
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The invention discloses a preparation method of diphenyl disulfide compounds. The preparation method comprises the following steps: stirring an isopropyl magnesium halide Grignard reagent and a substituted halogen benzene compound in an organic solvent at -78 DEG C to -20 DEG C for 30-90 minutes to obtain a thoroughly halogen-magnesium exchanged substituted phenyl Grignard reagent; and adding dichlorodisulfide into the reaction system, slowly heating to room temperature after the reaction is finished, quenching the reaction by using a saturated ammonium chloride aqueous solution, extracting byusing ethyl acetate or diethyl ether, drying by using anhydrous magnesium sulfate, and concentrating the organic phase to obtain the diphenyl disulfide compounds. According to the method, the diphenyl disulfide compounds are prepared by taking the phenyl Grignard reagent as a raw material through a one-pot method, and has the following advantages: the synthetic route is short, the preparation process is simple, the cost is low, the operation is easy, the yield is excellent, and the industrial production is easy.
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Paragraph 0051; 0052; 0053; 0054; 0055; 0056; 0057
(2020/10/21)
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- S-(4-Methoxyphenyl)-4-methoxybenzenesulfonothioate as a Promising Lead Compound for the Development of a Renal Carcinoma Agent
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Organosulfur compounds show cytotoxic potential towards many tumor cell lines. Disulfides and thiosulfonates act through apoptotic processes, inducing proteins associated with apoptosis, endoplasmic reticulum stress, and the unfolded protein response. Three p-substituted symmetric diaryl disulfides and three diaryl thiosulfonates were synthesized and analyzed for inhibition of tubulin polymerization and for human cancer cell cytotoxic activity against seven tumor cell lines and a non-tumor cell line. S-(4-methoxyphenyl)-4-methoxybenzenesulfonothioate (6) exhibited inhibition of tubulin polymerization and showed the best antiproliferative potential, especially against the 786-0 cell line, being six times more selective as compared with the non-tumor cell line. In addition, compound 6 was able to activate caspase-3 after 24 and 48 h treatments of the 786-0 cell line and induced cell-cycle arrest in the G2/M stage at the highest concentration evaluated at 24 and 48 h. Compound 6 was able to cause complete inhibition of proliferation, inducing the death of 786-0 cells, by increasing the number of cells at G2/M and greater activation of caspase-3.
- Nantes, Camilla I.,Pereira, Ingrid D.,Bai, Ruoli,Hamel, Ernest,Burnett, James C.,de Oliveira, Rodrigo J.,de F. C. Matos, Maria,Beatriz, Adilson,Yonekawa, Murilo K. A.,Perdomo, Renata T.,de Lima, Dênis P.,Bogo, Danielle,dos A. dos Santos, Edson
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p. 449 - 458
(2020/01/25)
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- TEMPO visible light photocatalysis: The selective aerobic oxidation of thiols to disulfides
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TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) is well-established in orangocatalysis that usually work in synergy with transition-metal catalysis or semiconductor photocatalysis. Here, TEMPO was turned into a visible light photocatalyst to conduct the selective aerobic oxidation of thiols into disulfides. With O2 as an oxidant, a mild and efficient protocol for the selective oxidation of thiols into disulfides including symmetrical and unsymmetrical ones with 5 molpercent of TEPMO as a photocatalyst was developed at room temperature under the irradiation of 460 nm blue LEDs. It was found that a complex formed between TEMPO and thiols underpinned the visible light activity and disulfides were obtained in very high isolated yields. This work suggests that TEMPO takes diverse roles in for photocatalytic selective oxidative transformations with O2 as the oxidant.
- Xu, Hui,Zhang, Yu-Fei,Lang, Xianjun
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supporting information
p. 1520 - 1524
(2019/12/09)
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- Visible-light photocatalytic selective aerobic oxidation of thiols to disulfides on anatase TiO2
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This work presents the visible-light photocatalytic selective oxidation of thiols to disulfides with molecular oxygen (O2) on anatase TiO2. The high specific surface area of anatase TiO2 proved to be especially critical in
- Xu, Hui,Shi, Ji-Long,Lyu, Shaoshuai,Lang, Xianjun
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p. 1468 - 1473
(2020/04/29)
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- Ligand-Free Copper(I)-Mediated Cross-Coupling Reactions of Organostannanes with Sulfur Electrophiles
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The synthesis of aryl thioether through the cross-coupling of C-S bond is a highly attractive area of research due to the prevalence of aryl thioether in bioactive natural products, functional materials, agrochemicals, and pharmaceutically active compound
- Zhu, Feng,Chen, Zhenhao,Walczak, MacIej A.
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p. 11942 - 11951
(2020/10/12)
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- Method for synthesizing symmetric disulfide compound by taking aryl hydrazine and S8 as raw materials
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The invention relates to a method for synthesizing a symmetric disulfide compound by taking aryl hydrazine and S8 as raw materials, and belongs to the technical field of organic synthesis; the methodis characterized in that the aryl hydrazine compound and S8 are used as substrates to react in a reaction solvent under the promotion of alkali to generate the symmetric disulfide organic compound, the reaction gas atmosphere is air or oxygen, the reaction temperature is 40 DEG C-100 DEG C, and the reaction time is 4-24 hours. The synthesis steps are simple, the reaction conditions are mild, S8 which is widely distributed in nature, low in price and easy to obtain is used as a sulfur source, S-S bonds can be constructed only under the promotion of alkali without transition metal catalysis, theyield is as high as 95%, the applicable reaction substrate range is wide, the operation is simple and feasible, the synthesis cost is low, the environmental pollution is small, and a new thought is provided for the synthesis of the symmetric disulfide organic compound.
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Paragraph 0041-0044
(2020/11/23)
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- Electrochemically Catalyzed Newman-Kwart Rearrangement: Mechanism, Structure-Reactivity Relationship, and Parallels to Photoredox Catalysis
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The facilitation of redox-neutral reactions by electrochemical injection of holes and electrons, also known as "electrochemical catalysis", is a little explored approach that has the potential to expand the scope of electrosynthesis immensely. To systematically improve existing protocols and to pave the way toward new developments, a better understanding of the underlying principles is crucial. In this context, we have studied the Newman-Kwart rearrangement of O-arylthiocarbamates to the corresponding S-aryl derivatives, the key step in the synthesis of thiophenols from the corresponding phenols. This transformation is a particularly useful example because the conventional method requires temperatures up to 300 °C, whereas electrochemical catalysis facilitates the reaction at room temperature. A combined experimental-quantum chemical approach revealed several reaction channels and rendered an explanation for the relationship between the structure and reactivity. Furthermore, it is shown how rapid cyclic voltammetry measurements can serve as a tool to predict the feasibility for specific substrates. The study also revealed distinct parallels to photoredox-catalyzed reactions, in which back-electron transfer and chain propagation are competing pathways.
- Roesel, Arend F.,Ugandi, Mihkel,Huyen, Nguyen Thi Thu,Májek, Michal,Broese, Timo,Roemelt, Michael,Francke, Robert
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supporting information
p. 8029 - 8044
(2020/07/25)
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- Directed oxidative coupling of thiols in the synthesis of unsymmetrical disulfides
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Oxidative coupling of two different thiols bearing aliphatic, alicyclic, aromatic, and hetero-aromatic moieties promoted by mild oxidizing agents, viz., sterically hindered o-benzo(imino)-quinones, carried out in N-methylpyrrolidone at room temperature led to unsymmetrical disulfides. Among the studied oxidizers, the most active was 3,6-di-tert-butyl-o-benzoquinone, which, in contrast to 3,5-di-tert-butyl-o-benzoquinone, was not involved in the Michael addition. Under the optimal reaction conditions, the yields of the target unsymmetrical disulfides reach 81%.
- Berberova, N. T.,Burmistrova, D. A.,Smolyaninov, I. V.
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p. 990 - 995
(2020/06/17)
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- First use of an organobismuth reagent in C(sp3)–S bond formation: Access to aryl cyclopropyl sulfides via copper-catalyzed S–Cyclopropylation of thiophenols using tricyclopropylbismuth
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The direct S-cyclopropylation of thiophenols using tricyclopropylbismuth is reported. The reaction is catalyzed by copper(II) acetate and operates under mild conditions to afford the corresponding aryl cyclopropyl sulfides in moderate to good yields. This reaction represents the first use of an organobismuth reagent in C(sp3)–S bond formation.
- Benoit, Emeline,Bueno, Bianca,Choinière, Catherine,Gagnon, Alexandre
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supporting information
p. 72 - 77
(2019/05/15)
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- Synthesis and nano-Pd catalyzed chemoselective oxidation of symmetrical and unsymmetrical sulfides
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A highly chemoselective, efficient and nano-Pd catalyzed protocol for the rapid construction of sulfoxides and sulfones via the oxidation of symmetrical and unsymmetrical sulfides using H2O2 as an oxidant has been developed, respectively. The ready availability of starting materials, easy recovery and reutilization of the catalyst, wide substrate scope, and high yields make this protocol an attractive alternative. The process also involves the metal-free and microwave-promoted synthesis of symmetrical diarylsulfides, and FeCl3-mediated preparation of symmetrical diaryldisulfides through the reaction of arenediazonium tetrafluoroborates with Na2S·9H2O as a sulfur source. In addition, unsymmetrical sulfides were generated via the K2CO3-mediated reaction of arenediazonium tetrafluoroborates with symmetrical disulfides.
- Li, Xing,Du, Jia,Zhang, Yongli,Chang, Honghong,Gao, Wenchao,Wei, Wenlong
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p. 3048 - 3055
(2019/03/21)
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- Utilizing 2-phenylpropanal as coupling partner for C-S bond formation via sequential thioarylation and decarbonylation process: A novel strategy for the synthesis of aryl alkyl sulfides
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In this study, first direct access to aryl alkyl sulfides employing 2-phenylpropanal as coupling partner is reported. Diaryl disulfides react with this aldehyde in the presence of morpholine and produce the corresponding sulfide products in high yields. In another part, disulfides are in situ generated in the reaction mixture from aryl halides/CuI/Cyanodithioformate and coupled with 2-phenylpropanal to access aryl alkyl sulfides.
- Shaikhi Shahidzadeh, Elham,Nowrouzi, Najmeh,Abbasi, Mohammad
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- Method for pipeline continuous production of aryl disulfide ether compounds
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The invention discloses a method for pipeline continuous production of aryl disulfide ether compounds, wherein a device comprises a pipe reactor, a raw material storage tank and a gas storage bottle,the method comprises the following steps: adding aryl sulfonyl chloride, a catalyst, water and an alcohol solvent to prepare a material solution, and storing the material solution in the raw materialstorage tank; putting a SO2 gas in the gas storage bottle; when the reaction is started, fully filling the pipe reactor with the alcohol solvent, and then respectively pumping the material solution and the SO2 gas into the pipe reactor for reaction; absorbing a gas discharged by the pipe reactor by an alkali water solution; and removing the solvent from a reaction product discharged from the pipereactor, adding water, filtering, and drying filter cake to obtain the aryl disulfide ether compounds. The method can realize pipeline continuous production of the aryl disulfide ether compounds, thereaction conditions are simple, the post-treatment is convenient, and the yield is high.
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Paragraph 0040-0051
(2019/07/04)
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- Cyclic telluride reagents with remarkable glutathione peroxidase-like activity for purification-free synthesis of highly pure organodisulfides
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Monoamino cyclic tellurides with a five- or six-membered ring structure and their derivatives were developed as a new class of catalyst for the oxidation of organothiols to organodisulfides in a glutathione peroxidase-like catalytic reaction. Quantitative conversion and high reaction rate were achieved by performing the reaction in an organic-aqueous segmented microflow system. Importantly, the process circumvented product purification, which is a major limitation of current organodisulfide synthetic methods.
- Arai, Kenta,Osaka, Yuui,Haneda, Masahiro,Sato, Yuumi
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p. 3647 - 3655
(2019/07/22)
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- T BuOK-triggered bond formation reactions
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Recently, inexpensive and readily available tBuOK has seen widespread use in transition-metal-free reactions. Herein, we report the use of tBuOK for S-S, S-Se, NN and CN bond formations, which significantly extends the scope of tBuOK in chemical synthesis. Compared with traditional methods, we have realized mild and general methods for disulfide, azobenzenes imine etc. synthesis.
- Xu, Yulong,Shi, Xiaonan,Wu, Lipeng
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p. 24025 - 24029
(2019/08/13)
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- Biocatalytic synthesis of diaryl disulphides and their bio-evaluation as potent inhibitors of drug-resistant Staphylococcus aureus
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Staphylococcus aureus is a WHO Priority II pathogen for its capability to cause acute to chronic infections and to resist antibiotics, thus severely impacting healthcare systems worldwide. In this context, it is urgently desired to discover novel molecules to thwart the continuing emergence of antimicrobial resistance. Disulphide containing small molecules has gained prominence as antibacterials. As their conventional synthesis requires tedious synthetic procedure and sometimes toxic reagents, a green and environmentally benign protocol for their synthesis has been developed through which a series of molecules were obtained and evaluated for antibacterial activity against ESKAPE pathogen panel. The hit compound was tested for cytotoxicity against Vero cells to determine its selectivity index and time-kill kinetics was determined. The activity of hit was determined against a panel of S. aureus multi-drug resistant clinical isolates. Also, its ability to synergize with FDA approved drugs was tested as was its ability to reduce biofilm. We identified bis(2-bromophenyl) disulphide (2t) as possessing equipotent antimicrobial activity against S. aureus including MRSA and VRSA strains. Further, 2t exhibited a selectivity index of 25 with concentration-dependent bactericidal activity, synergized with all drugs tested and significantly reduced preformed biofilm. Taken together, 2t exhibits all properties to be positioned as novel scaffold for anti-staphylococcal therapy.
- Saima,Soni, Isha,Lavekar, Aditya G.,Shukla, Manjulika,Equbal, Danish,Sinha, Arun K.,Chopra, Sidharth
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p. 171 - 178
(2019/01/04)
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- Natural gallic acid catalyzed aerobic oxidative coupling with the assistance of MnCO3 for synthesis of disulfanes in water
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The formation of S-S bonds has great significance and value in synthetic chemistry and bioscience. To pursue a sustainable approach for such a synthesis, an aerobic oxidative coupling method for the efficient preparation of organic disulfanes, using a low-toxic natural gallic acid as an organocatalyst, inexpensive MnCO3 as a cocatalyst, O2 as the terminal oxidant and water as the solvent, has been successfully developed. Such metal-organic cooperative catalytic protocol provided an access to various symmetrical and unsymmetrical disulfanes in up to 99% yield. Gram scale synthesis with practical convenience and low loading of catalysts further illustrates the practicability of our method.
- Song, Lijuan,Li, Wenhao,Duan, Wenxue,An, Jichao,Tang, Shanyu,Li, Longjia,Yang, Guanyu
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supporting information
p. 1432 - 1438
(2019/03/26)
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- Probing the Proton-Coupled Electron-Transfer (PCET) Reactivity of a Cross-Conjugated Cruciform Chromophore by Redox-State-Dependent Fluorescence
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Proton-coupled electron transfer (PCET) reactions are of great importance in synthetic chemistry and in biology, but the acquisition of kinetic information for these reactions is often difficult. Herein, we report the synthesis of a new PCET reagent, showing redox-state dependent fluorescence, by merging the concept of cross-conjugated cruciform chromophores with the strategy of imposing redox activity and Br?nsted basicity to aromatic compounds by substitution with guanidino groups. The compound is isolated and characterized in all stable states—reduced, twofold and fourfold protonated and twofold oxidized—and then applied in PCET reactions by using its redox-state dependent fluorescence signal for kinetic measurements.
- Wagner, Conrad,Hübner, Olaf,Kaifer, Elisabeth,Himmel, Hans-J?rg
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supporting information
p. 3781 - 3785
(2019/02/20)
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- Fenton-Inspired C-H Functionalization: Peroxide-Directed C-H Thioetherification
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Substoichiometric iron mediates the thioetherification of unactivated aliphatic C-H bonds directed by resident silylperoxides. Upon exposure to a catalytic amount of iron(II) triflate, TIPS-protected peroxides bearing primary, secondary, and tertiary C-H sites undergo chemoselective thioetherification of remote C-H bonds with diaryl disulfides. The reaction demonstrates a broad substrate scope and functional group tolerance without the use of any noble metal additives. Mechanistic experiments suggest that the reaction proceeds through 1,5-H atom abstraction by a hydroxyl radical generated with iron.
- Groendyke, Brian J.,Modak, Atanu,Cook, Silas P.
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p. 13073 - 13091
(2019/10/10)
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- Direct C-H sulfenylation of quinoxalinones with thiols under visible-light-induced photocatalyst-free conditions
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A photocatalyst-free visible-light-promoted sulfenylation of quinoxalinones with thiols via cross-dehydrogenative coupling was developed. This protocol allowed the direct formation of diverse 3-sulfenylquinoxalin-2(1H)-ones under metal- and catalyst-free
- Teng, Qing-Hu,Yao, Yan,Wei, Wen-Xiu,Tang, Hai-Tao,Li, Jia-Rong,Pan, Ying-Ming
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supporting information
p. 6241 - 6245
(2019/12/03)
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- Unsymmetrical Disulfides Synthesis via Sulfenium Ion
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An umpolung approach for the synthesis of unsymmetrical disulfides via sulfenium ion is reported. In situ generated electrophilic sulfenium ion from electron-rich thiols reacted with second thiols to yield unsymmetrical disulfides. Using an iodine catalyst and 4-dimethylaminopyridine (DMAP)/water as promoter, the target syntheses were achieved in one pot under aerobic condition.
- Parida, Amarchand,Choudhuri, Khokan,Mal, Prasenjit
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supporting information
p. 2579 - 2583
(2019/07/15)
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- Synthesis of aryl cyclopropyl sulfides through copper-promoted S-cyclopropylation of thiophenols using cyclopropylboronic acid
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The copper-promoted S-cyclopropylation of thiophenols using cyclopropylboronic acid is reported. The procedure operates under simple conditions to afford the corresponding aryl cyclopropyl sulfides in moderate to excellent yields. The reaction tolerates substitution in ortho-, meta- and para-substitution as well as electron-donating and electron-withdrawing groups. The S-cyclopropylation of a thiophenol was also accomplished using potassium cyclopropyl trifluoroborate.
- Benoit, Emeline,Fnaiche, Ahmed,Gagnon, Alexandre
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p. 1162 - 1171
(2019/06/08)
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- A novel dual-nano assisted synthesis of symmetrical disulfides from aryl/alkyl halides
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Here, we have reported a novel approach towards dual-nano assisted synthesis of disulfides from coupling of alkyl/aryl halides and sulfur nanoparticles. The indium oxide nanoparticles as catalyst expedite the conversion and sulfur nanoparticle notably enhances the miscibility, providing a faster, high yielding and cost-effective process in ethanol-water system. The method has synthetic advantages in terms of mild reaction framework, catalyst regeneration, and absence of any sulfide or polysulfide linkage as by-product leading to a column free synthesis. A variety of alkyl, aryl and heteroaryl symmetrical disulfides are obtained in good to excellent yields up to exceeding 98%.
- Devi, Namita,Hazarika, Sukanya,Gogoi, Prasanta,Barman, Pranjit
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supporting information
p. 1927 - 1938
(2018/07/21)
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- Magnetic iron oxide nanoparticles/K2S: a simple and scale-up method for the direct synthesis of symmetrical disulfides from aryl halides
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A simple, one-pot, efficient and novel protocol has been developed for direct synthesis of symmetrical organic disulfides by domino reaction of aryl halides and K2S in the presence of magnetic Fe3O4 nanoparticles as a readily available, highly efficient and recyclable catalyst. A variety of diaryl disulfides can be obtained in good-to-excellent yields up to 98%.
- Soleiman-Beigi, Mohammad,Mohammadi, Keivan,Mohammadi, Fariba
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p. 1545 - 1550
(2018/06/21)
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- Stereoretentive C(sp3)-S Cross-Coupling
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We report a stereoretentive cross-coupling reaction of configurationally stable nucleophiles with disulfide and N-sulfenylsuccinimide donors promoted by Cu(I). We demonstrate the utility of this method in the synthesis of thioglycosides derived from simple alkyl and aryl thiols, thioglycosides, and in the glycodiversification of cysteine residues in peptides. These reactions operate well with carbohydrate substrates containing common protective groups and reagents with free hydroxyl and secondary amide functionalities under standardized conditions. Competition experiments in combination with computational DFT studies established that the putative anomeric intermediate is an organocopper species that is configurationally stable and resistant to epimerization due to its short lifetime. The subsequent reductive elimination from the Cu(III) intermediate is rapid and stereoretentive. Taken together, the glycosyl cross-coupling is ideally suited for late stage glycodiversification and bioconjugation under highly controlled installation of the aliphatic carbon-sulfur bonds.
- Zhu, Feng,Miller, Eric,Zhang, Shuo-Qing,Yi, Duk,O'Neill, Sloane,Hong, Xin,Walczak, Maciej A.
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supporting information
p. 18140 - 18150
(2019/01/04)
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- Unsymmetrical Disulfide Synthesis through Photoredox Catalysis
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A facile and eco-friendly visible light-mediated synthesis of symmetrical and unsymmetrical disulfides using tris[2-phenylpyridinato-C2,N]iridium(III) under additive and oxidant free conditions has been disclosed. The developed method is very mild, several functional group tolerant and highly atom economical requiring extremely low amount of catalyst loading (0.5 mol%). (Figure presented.).
- Dethe, Dattatraya H.,Srivastava, Aparna,Dherange, Balu D.,Kumar, B. Vijay
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supporting information
p. 3020 - 3025
(2018/08/23)
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- An Organodiselenide with Dual Mimic Function of Sulfhydryl Oxidases and Glutathione Peroxidases: Aerial Oxidation of Organothiols to Organodisulfides
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A novel organodiselenide, which mimics sulfhydryl oxidases and glutathione peroxidase (GPx) enzymes for oxidation of thiols by oxygen and hydrogen peroxide, respectively, into disulfides has been presented. The developed catalyst oxidizes an array of organothiols into respective disulfides in practical yields by using aerial O2 to avoid any reagents/additives, base, and light source. The synthesized diselenide also catalyzes the reduction of hydrogen peroxide into water by following the GPx enzymatic catalytic cycle with a reduction rate of 49.65 ± 3.7 μM·min-1.
- Rathore, Vandana,Upadhyay, Aditya,Kumar, Sangit
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supporting information
p. 6274 - 6278
(2018/10/05)
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- Photo-induced thiol coupling and C-H activation using nanocrystalline lead-halide perovskite catalysts
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The use of photon energy to promote chemical transformations offers versatile control of reaction kinetics and progress. Over the past decade, many photoactive transition-metal complexes and organic chromophores were developed to catalyze chemical transformations, enabling a myriad of reactions and compounds that were previously inaccessible via traditional synthetic methods. Here, we demonstrate the photocatalytic oxidative coupling of organic thiols using cesium lead halide perovskite nanocrystals as photocatalysts. The photo-catalyzed thiol coupling reactions selectively produced symmetric and unsymmetrical disulfides in high yields (68-96% isolated yields). Additionally, we discovered a perovskite-catalyzed phosphonylation of tertiary amines via visible-light-mediated cross-dehydrogenative coupling reaction, and obtained good isolated yields (50-96%). The variety of visible-light-induced photocatalytic processes that perovskite nanocrystals are capable of, coupled with their facile preparation, easily tunable redox potentials, high catalytic efficiency and reusability, presents great opportunities for their future applications in green and sustainable organic synthesis.
- Wu, Wen-Bin,Wong, Ying-Chieh,Tan, Zhi-Kuang,Wu, Jie
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p. 4257 - 4263
(2018/08/24)
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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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- PTAB mediated open air synthesis of sulfonamides, thiosulfonates and symmetrical disulfanes
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A facile methodology has been described which has successfully simplified the generation of sulfonamides, thiosulfonates and symmetric disulfanes. This “trio” of reactions occur in an open air metal free atmosphere and has also been scaled up to grams making it suitable for commercialization. The reactions also have been successfully carried out with asymmetric variants, thus contributing to the chiral pool. The user friendly “trio” enables easy generation of these versatile sulfur analogues and the reaction condition employed depict an economic outline.
- Sarkar, Debayan,Ghosh, Manoj Kumar,Rout, Nilendri
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p. 2360 - 2364
(2018/05/24)
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- Deep Eutectic Solvents as Reaction Media for the Palladium-Catalysed C?S Bond Formation: Scope and Mechanistic Studies
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A unique jigsaw catalytic system based on deep eutectic solvents and palladium nanoparticles where C?S bonds are formed from aryl boronic acids and sodium metabisulfite, is introduced. The functionalization step is compatible with a broad spectrum of reagents such as nucleophiles, electrophiles or radical scavengers. This versatile approach allows the formation of different types of products in an environmentally friendly medium by selecting the components of the reaction, which engage one with another as pieces in a jigsaw. This simple procedure avoids the use of toxic volatile organic solvents allowing the formation of complex molecules in a one-pot reaction under mild conditions. Despite the fact that only 1 mol % of metal loading is used, the recyclability of the catalytic system is possible. Kinetic experiments were performed and the reaction order for all reagents, catalyst and ligand was determined. The obtained results were compared to palladium nanocrystals of different known shapes in order to shed some light on the properties of the catalyst.
- Marset, Xavier,Guillena, Gabriela,Ramón, Diego J.
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supporting information
p. 10522 - 10526
(2017/08/10)
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- Europhtal (8020) efficiently catalyzes the aerobic oxidation of in situ generated thiols to symmetric disulfides (disulfanes)
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Efficient, odorless and scalable synthetic protocols have been introduced for the preparation of symmetric alkyl disulfides by treatment of the corresponding organic halides with thiourea and NaHCO3in the presence of commercially available Europhtal catalyst (8020) in both H2O and poly ethylene glycol (PEG-200) media at 80–90 °C. Structurally diverse primary, secondary, allylic and benzylic halides were examined successfully whereas, the result with tert-butyl bromide was not satisfactory. Also, another procedure has been introduced for achieving symmetric aryl disulfides in high yields by reacting aryl halides, thiourea and NaHCO3in PEG-200 at 115–120 °C using CuI along with Europhtal catalysts. The results showed that the aerobic oxidation of in situ generated thiols proceeded efficiently in the presence of Europhtal catalyst giving the symmetric disulfide without contamination by symmetric sulfide side-product.
- Abbasi, Mohammad,Sabet, Askar,Sabet, Askar
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- Ligand-free copper-catalysed direct synthesis of diaryl sulfides and diaryl disulfides in wet poly(ethylene glycol)
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An improved protocol has been developed for the one-pot CuI-catalysed preparation of symmetric diaryl sulfides from their available aryl halides in the presence of thiourea as sulfur transfer agent and in the absence of both ligand and organic solvent. This catalytic system was also used for the high-yielding preparation of diaryl disulfides in the presence of C2Cl6 as oxidant.
- Nowrouzi, Najmeh,Abbasi, Mohammad,Latifi, Hadis
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- Metal–organic framework MOF-199-catalyzed direct and one-pot synthesis of thiols, sulfides and disulfides from aryl halides in wet polyethylene glycols (PEG 400)
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A highly porous metal–organic frame work Cu3 BTC2 (copper(II)-benzene-1,3,5-tricarboxylate) that is known as MOF-199 was synthesized from the reaction of 1,3,5-benzenetricarboxylic acid and Cu(OAc)2·H2O by a solvothermal method and characterized by several techniques including FT-IR, XRD, EDX and scanning electron microscopy. The MOF-199 used as an efficient catalyst for one-pot synthesis of thiols by domino reactions of aryl halides and thiourea, and subsequently conversion to aryl alkyl sulfides and diaryl disulfides in polyethylene glycols (PEGs). A variety of aryl alkyl sulfides can be obtained in good to excellent yields in a relatively short reaction time and in the presence of the trace amount of catalyst. Also, the catalyst can be separated from the reaction mixture by decanting, and be reused without significant degradation in catalytic activity.
- Soleiman-Beigi, Mohammad,Sadeghizadeh, Fatemeh,Basereh, Ali
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p. 572 - 583
(2017/09/27)
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- Reusable cobalt-phthalocyanine in water: Efficient catalytic aerobic oxidative coupling of thiols to construct S-N/S-S bonds
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A new aerobic oxidative coupling of thiols in water to construct sulfenamides or disulfides was developed, utilizing cobalt(ii)phthalocyanine-tetra-sodium sulfonate as the catalyst and O2 as the oxidant. The mother liquor could be recycled up to 20 times with negligible loss of activity and only a minor decrease of product yield.
- Dou, Yingchao,Huang, Xin,Wang, Hao,Yang, Liting,Li, Heng,Yuan, Bingxin,Yang, Guanyu
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supporting information
p. 2491 - 2495
(2017/07/17)
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- Photoinduced Oxidative Cross-Coupling for O-S Bond Formation: A Facile Synthesis of Alkyl Benzenesulfonates
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We have developed a photoinduced oxidative cross-coupling of thiophenols with alcohols for O-S bond formation. The protocol uses visible light, a metal-free photocatalyst, and oxygen as the oxidant for the selective synthesis of alkyl benzenesulfonates; no ligand co-additive is necessary. Mechanistic studies suggested that the disulfide and alkyl benzenesulfinate are involved as intermediates and that the transformation proceeds by a radical pathway.
- Singh, Atul K.,Yi, Hong,Zhang, Guoting,Bian, Changliang,Pei, Pengkun,Lei, Aiwen
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supporting information
p. 1558 - 1563
(2017/08/11)
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- Oxidative dimerization of thiols to disulfide using recyclable magnetic nanoparticles
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Abstract: Dimerization of thiol groups to disulfide is an important transformation in chemical processes. In this study, magnetic ion exchanged Montmorillonite-k10 was synthesized and characterized using FTIR, X-ray diffraction and scanning electron microscope techniques. Then, the application of the synthesized catalyst as an efficient oxidizing agent was evaluated in oxidative dimerization of different thiols to corresponding disulfides under optimal reaction conditions. The reaction was easily performed with aromatic, aliphatic and heterocyclic thiols. The magnetic catalyst was easily recovered by applying an external magnet and, further, was reused in successive reactions. Graphical Abstract: [Figure not available: see fulltext.]
- Masnabadi, Nasrin,Ghasemi, Mohammad Hadi,Beyki, Mostafa Hossein,Sadeghinia, Mohammad
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p. 1609 - 1618
(2017/02/15)
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- Synthesis and in vitro biological evaluation of thiosulfinate derivatives for the treatment of human multidrug-resistant breast cancer
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Organosulfur compounds derived from Allium vegetables have long been recognized for various therapeutic effects, including anticancer activity. Allicin, one of the main biologically active components of garlic, shows promise as an anticancer agent; however, instability makes it unsuitable for clinical application. The aim of this study was to investigate the effect of stabilized allicin derivatives on human breast cancer cells in vitro. In this study, a total of 22 stabilized thiosulfinate derivatives were synthesized and screened for their in vitro antiproliferative activities against drug-sensitive (MCF-7) and multidrug-resistant (MCF-7/Dx) human adenocarcinoma breast cancer cells. Assays for cell death, apoptosis, cell cycle progression and mitochondrial bioenergetic function were performed. Seven compounds (4b, 7b, 8b, 13b, 14b, 15b and 18b) showed greater antiproliferative activity against MCF-7/Dx cells than allicin. These compounds were also selective towards multidrug-resistant (MDR) cells, a consequence attributed to collateral sensitivity. Among them, 13b exhibited the greatest anticancer activity in both MCF-7/Dx and MCF-7 cells, with IC50 values of 18.54±0.24 and 46.50±1.98 μmol/L, respectively. 13b altered cellular morphology and arrested the cell cycle at the G2/M phase. Additionally, 13b dose-dependently induced apoptosis, and inhibited cellular mitochondrial respiration in cells at rest and under stress. MDR presents a significant obstacle to the successful treatment of cancer clinically. These results demonstrate that thiosulfinate derivatives have potential as novel anticancer agents and may offer new therapeutic strategies for the treatment of chemoresistant cancers.
- Roseblade, Ariane,Ung, Alison,Bebawy, Mary
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p. 1353 - 1368
(2017/10/10)
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- Visible light mediated reductions of ethers, amines and sulfides
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Visible light-mediated photoredox catalysis enables the chemoselective reduction of activated carbon–heteroatom bonds as a function of reduction potential. The expansion of the scope of C–X bond reductions towards less activated motifs, such as ethers, amines and sulfides, is important to both organic synthesis and macromolecular degradation method development. In the present report, exploration of photoredox catalysis in alcoholic solvents mediated a decrease in the super-stoichiometric use of iPr2NEt and HCO2H in the reduction of α-keto ethers, amines and sulfides. Additionally, in the absence of fragmentation, [Formula presented] bond formation was afforded, suggesting an intermediate ketyl radicals are present in these transformations.
- Monos, Timothy M.,Magallanes, Gabriel,Sebren, Leanne J.,Stephenson, Corey R.J.
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p. 240 - 248
(2016/07/21)
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- Aryl diazonium salt and thioacetamide: A catalyst free, efficient blend of an inexpensive arylating agent with "s" surrogate for sulphide synthesis
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Novel, facile C-S and S-S bond coupling reactions were achieved by using an aryl diazonium salt as an arylating agent and thioacetamide as a sulphur surrogate. The reaction proceeds smoothly at room temperature without using any transition metal catalyst, ligand or base. Aryl diazonium salts undergo rapid reactions with thioacetamide at room temperature to give the desired products in a much shorter period than the previously reported metal catalysed protocols.
- Bhojane, Jeevan Manohar,Sarode, Sachin Ashok,Nagarkar, Jayashreemilind
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p. 90046 - 90050
(2016/10/07)
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- Metal Organic Framework 199- Catalyzed Domino Sulfur-Coupling and Transfer Reactions: The Direct Synthesis of Symmetric Diaryl Disulfides from Aryl Halides
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Abstract: A highly porous metal–organic framework Cu3 BTC2 (copper(II)-benzene-1,3,5-tricarboxylate) that known as MOF-199 was synthesized, and characterized by common methods including, FT-IR, XRD, EDX, SEM and then used as an efficient and recyclable catalyst for the direct synthesis of symmetric organic disulfides. A variety of symmetric diaryl disulfides with high chemoselectivity can be obtained by domino reaction of aryl halides (and tosylates) and potassium 5-methyl-1,3,4-oxadiazole-2- thiolate, as the base and sulfur-transfer reagent, in the presence of MOF-199. Graphical Abstract: [Figure not available: see fulltext.]
- Soleiman-Beigi, Mohammad,Mohammadi, Fariba
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p. 1497 - 1504
(2016/07/30)
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- Selective synthesis of organic sulfides or disulfides by solvent exchange from aryl halides and KSCN catalyzed by NiCl2·6H2O
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A method for selective synthesis of symmetric sulfides or disulfides from the reaction of aryl halides with KSCN by solvent exchange is introduced. Aryl halides were selectively converted to the symmetric disulfides or sulfides in high yields when they are treated with KSCN in the presence of NiCl2·6H2O and DMAP at 140?°C in DMF or poly ethylene glycol (PEG-200) respectively.
- Abbasi, Mohammad,Nowrouzi, Najmeh,Latifi, Hadis
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p. 112 - 117
(2016/09/07)
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