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Cobalt-iron magnetic composites as heterogeneous catalysts for the aerobic oxidation of thiols under alkali free conditions
Cobalt-iron magnetic composites prepared by the thermal treatment of an iron oxide-rich soil in the presence of sucrose and cobalt(II) sulfate are efficient heterogeneous catalysts for the liquid-phase aerobic oxidation of thiols into disulfides. The mate
Menini, Luciano,Pereira, Márcio C.,Ferreira, André C.,Fabris, José D.,Gusevskaya, Elena V.
p. 151 - 157
(2011)
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Electrochemical Oxidative Carbon-Atom Difunctionalization: Towards Multisubstituted Imino Sulfide Ethers
Ethers (C?O/S) are ubiquitously found in a wide array of functional molecules and natural products. Nonetheless, the synthesis of imino sulfide ethers, containing an N(sp2)=C(sp2)?O/S fragment, still remains a challenge because of it
Guan, Zhipeng,Zhu, Shuxiang,Wang, Siyuan,Wang, Huamin,Wang, Siyuan,Zhong, Xingxing,Bu, Faxiang,Cong, Hengjiang,Lei, Aiwen
p. 1573 - 1577
(2021)
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Dimsyl Anion Enables Visible-Light-Promoted Charge Transfer in Cross-Coupling Reactions of Aryl Halides
A methodology is reported for visible-light-promoted synthesis of unsymmetrical chalcogenides enabled by dimsyl anion in the absence of transition-metals or photoredox catalysts. The cross-coupling reaction between aryl halides and diaryl dichalcogenides proceeds with electron-rich, electron-poor, and heteroaromatic moieties. Mechanistic investigations using UV-Vis spectroscopy, time-dependent density functional theory (TD-DFT) calculations, and control reactions suggest that dimsyl anion forms an electron-donor-acceptor (EDA) complex capable of absorbing blue light, leading to a charge transfer responsible for generation of aryl radicals from aryl halides. This previously unreported mechanistic pathway may be applied to other light-induced transformations performed in DMSO in the presence of bases and aryl halides.
Pan, Lei,Cooke, Maria Victoria,Spencer, Amara,Laulhé, Sébastien
supporting information
p. 420 - 425
(2021/11/01)

Generation of Thiyl Radicals from Air-Stable, Odorless Thiophenol Surrogates: Application to Visible-Light-Promoted C-S Cross-Coupling
The synthetic versatility of thiophenols is offset by their airsensitivity and foul odor. It is demonstrated that S-aryl isothiouronium salts can be used as precursors to thiyl radicals, extending the practical benefits of these air-stable, odorless salts from ionic to single electron manifolds. The isothiouronium salts are accessed via Ni-catalyzed crosscoupling of (hetero)aryl iodides and thiourea and are isolated as freeflowing solids following anion exchange. Judicious choice of a redox-innocent counteranion enables use of these convenient thiophenol surrogates in radical processes, as is exemplified by the synthesis of nonsymmetrical diaryl thioethers via light-promoted S-arylation.
Ball, Liam T.,Maggi, Lorenzo,Park, Mahri,Shepherd, William,Swan, Charlie,Taylor, Sophie
(2022/02/25)

Preparation method of symmetric disulfide bond-containing compound
The method comprises the following steps: adding a raw material and an oxidant to a reaction bottle containing a solvent; reacting 23W - 85W under the irradiation of 12 - 24h energy-saving lamps; and purifying the reaction product to obtain symmetrical disulfide bond-containing compounds. The raw material is mercaptan or thiophenol. The oxidizing agent is trichlorobromomethane, and the solvent is tetrahydrofuran. The method has the advantages of simple operation, high yield (70 - 90%), wide applicability, cheap and easily available raw materials, and provides a better way for the synthesis and production of symmetrical disulfide bond-containing compounds.
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(2021/11/21)

Synthesis and biological evaluation of disulfides as anticancer agents with thioredoxin inhibition
Altered redox homeostasis as a hallmark of cancer cells is exploited by cancer cells for growth and survival. The thioredoxin (Trx), an important regulator in maintaining the intracellular redox homeostasis, is cumulatively recognized as a promising target for the development of anticancer drugs. Herein, we synthesized 72 disulfides and evaluated their inhibition for Trx and antitumor activity. First, we established an efficient and fast method to screen Trx inhibitors by using the probe NBL-SS that was developed by our group to detect Trx function in living cells. After an initial screening of the Trx inhibitory activity of these compounds, 8 compounds showed significant inhibition activity against Trx. We then evaluated the cytotoxicity of these 8 disulfides, compounds 68 and 69 displayed high cytotoxicity to HeLa cells, but less sensitive to normal cell lines. Next, we performed kinetic studies of both two disulfides, 68 had faster inhibition of Trx than 69. Further studies revealed that 68 led to the accumulation of reactive oxygen species and eventually induced apoptosis of Hela cells via inhibiting Trx. The establishment of a method for screening Trx inhibitors and the discovery of 68 with remarkable Trx inhibition provide support for the development of anticancer candidates with Trx inhibition.
Wei, Xiangxu,Zhong, Miao,Wang, Song,Li, Lexun,Song, Zi-Long,Zhang, Junmin,Xu, Jianqiang,Fang, Jianguo
(2021/03/24)

Metal-free chalcogenation of cycloketone oxime esters with dichalcogenides
We report the metal-free chalcogenation of cycloketone oxime esters with dichalcogenides via a radical process. Because of the metal-free condition and use of readily accessible dichalcogenides, this method is an effective and green strategy for the synthesis of chalcogen-substituted butyronitrile.
Ji, Liangshuo,Qiao, Jiamin,Liu, Junjie,Tian, Miaomiao,Lu, Kui,Zhao, Xia
supporting information

(2021/06/15)

Electrochemical Thiolation and Borylation of Arylazo Sulfones with Thiols and B2pin2
An efficient electrochemical synthesis approach of various unsymmetrical thioethers and arylboronates has been developed. Bench stable arylazo sulfones were used as radical precursors for carbon-heteroatom bond formation under electrochemical conditions. Moreover, the scalability of this approach was evaluated by performing the electrochemical thiolation and borylation of arylazo sulfones with thiols and B2pin2 on a gram scale. This protocol not only avoided the use of stoichiometric oxidants, metal catalysts, activating agents and even added bases, but also exhibited favorable functional group tolerance. (Figure presented.).
Wang, Rongkang,Chen, Fangming,Jiang, Lvqi,Yi, Wenbin
supporting information
p. 1904 - 1911
(2021/02/12)

Copper-catalyzedortho-selective direct sulfenylation ofN-aryl-7-azaindoles with disulfides
A copper-catalyzed direct C-H chalcogenation ofN-aryl-azaindoles with disulfides is described. This transformation was performed using Earth abundant Cu(OAc)2as a catalyst, benzoic acid as an additive, air as a terminal oxidant, and readily available diaryl and dialkyldisulfides (or diselenide) as chalcogenation reagents. High functional group tolerance and excellent regioselectivity are demonstrated by the efficient preparation of a wide range ofortho-sulfenylation-7-azaindoles.
Ru-Jian, Yu,Chun-Yan, Zhang,Xiang, Zhou,Xiong, Yan-Shi,Duan, Xue-Min
supporting information
p. 2901 - 2906
(2021/04/14)

Forging C?S(Se) Bonds by Nickel-catalyzed Decarbonylation of Carboxylic Acid and Cleavage of Aryl Dichalcogenides
A nickel-catalyzed decarbonylation of carboxylic acids cross-coupling protocol has been developed for the straightforward C?S(Se) bond formation. This reaction is promoted by a commercially-available, user-friendly, inexpensive, air and moisture-stable nickel precatalyst. Various carboxylic acids and a wide range of aryl dichalcogenide substrates were tolerated in this process which afforded products in good to excellent yields. In addition, the present reaction can be conducted on gram scale in good yield.
Zhou, Jing-Ya,Zhu, Yong-Ming
p. 2452 - 2461
(2021/06/28)

Sequential C-H activation enabled expedient delivery of polyfunctional arenes
Modular construction of polyfunctional arenes from abundant feedstocks stands as an unremitting pursue in synthetic chemistry, accelerating the discovery of drugs and materials. Herein, using the multiple C-H activation strategy with versatile imidate esters, the expedient delivery of molecular libraries of densely functionalized sulfur-containing arenes was achieved, which enabled the concise construction of biologically active molecules, such as Bipenamol.
Cai, Xiaoqing,Chen, Qian,Chen, Xiaojian,Gao, Yang,Huo, Yanping,Li, Xianwei,Ouyang, Wensen,Rao, Jianhang,Wang, Jie
supporting information
p. 8075 - 8078
(2021/08/20)

Visible Light Induced Reduction and Pinacol Coupling of Aldehydes and Ketones Catalyzed by Core/Shell Quantum Dots
We present an efficient and versatile visible light-driven methodology to transform aryl aldehydes and ketones chemoselectively either to alcohols or to pinacol products with CdSe/CdS core/shell quantum dots as photocatalysts. Thiophenols were used as proton and hydrogen atom donors and as hole traps for the excited quantum dots (QDs) in these reactions. The two products can be switched from one to the other simply by changing the amount of thiophenol in the reaction system. The core/shell QD catalysts are highly efficient with a turn over number (TON) larger than 4 × 104 and 4 × 105 for the reduction to alcohol and pinacol formation, respectively, and are very stable so that they can be recycled for at least 10 times in the reactions without significant loss of catalytic activity. The additional advantages of this method include good functional group tolerance, mild reaction conditions, the allowance of selectively reducing aldehydes in the presence of ketones, and easiness for large scale reactions. Reaction mechanisms were studied by quenching experiments and a radical capture experiment, and the reasons for the switchover of the reaction pathways upon the change of reaction conditions are provided.
Xi, Zi-Wei,Yang, Lei,Wang, Dan-Yan,Feng, Chuan-Wei,Qin, Yufeng,Shen, Yong-Miao,Pu, Chaodan,Peng, Xiaogang
p. 2474 - 2488
(2021/02/05)

Transformation of arylboronic acids with sodium thiosulfate into organodisulfides catalyzed by a recyclable polyoxometalate-based Cr(iii) catalyst
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
supporting information
p. 6059 - 6064
(2021/08/23)

CARBORANE HYDROXAMIC ACID MATRIX METALLOPROTEINASE INHIBITORS AND AGENTS FOR BORON NEUTRON CAPTURE THERAPY
Disclosed herein are novel carborane hydroxamic acid matrix metalloproteinase ("MMP") inhibitors and agents bearing borane-containing moieties and methods for their use in treating or preventing a disease, such as cancer and rheumatoid arthritis. In parti
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Paragraph 0066; 00114

(2020/01/24)

Carborane-Containing Matrix Metalloprotease (MMP) Ligands as Candidates for Boron Neutron-Capture Therapy (BNCT)
Based on the previously reported potent and selective sulfone hydroxamate inhibitors SC-76276, SC-78080 (SD-2590), and SC-77964, potent MMP inhibitors have been designed and synthesized to append a boron-rich carborane cluster by employing click chemistry
Lutz, Marlon R.,Flieger, Sebastian,Colorina, Andre,Wozny, John,Hosmane, Narayan S.,Becker, Daniel P.
p. 1897 - 1908
(2020/09/01)

Visible-light induced decarboxylative coupling of redox-active esters with disulfides to construct C-S bonds
A novel method has been established for the construction of C-S bonds using redox-active esters with disulfides in the presence of Ru-photoredox catalyst. This method exhibits remarkable functional group tolerance across a wide scope of substrates. Under
Xiao, Zhiwei,Wang, Lu,Wei, Junjie,Ran, Chongzhao,Liang, Steven H.,Shang, Jingjie,Chen, Guang-Ying,Zheng, Chao
supporting information
p. 4164 - 4167
(2020/04/22)

Visible-light photocatalytic selective aerobic oxidation of thiols to disulfides on anatase TiO2
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
p. 1468 - 1473
(2020/04/29)

TEMPO visible light photocatalysis: The selective aerobic oxidation of thiols to disulfides
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
supporting information
p. 1520 - 1524
(2019/12/09)

Extended Pummerer fragmentation mediated by carbon dioxide and cyanide
Pummerer rearrangement reactions generate sulfur (II) oxidation state from sulfur (IV) starting materials in the presence of activating reagents. We found unprecedented transformation of vinyl sulfoxide; disulfide formation reactions mediated by atmospheric pressure of carbon dioxide in extended Pummerer rearrangement reactions. Only under CO2 atmosphere, we observed moderate to high yields of disulfide starting from sulfur (IV) starting materials. Investigations on the reaction mechanism revealed that the degradation of the starting materials and the products was significant in the absence of CO2. Further evidence for the suggested reaction mechanism was obtained by a cross-over experiment and a radical trapping reagent.
Liu, Jian,Kragh, Rasmus R.,Kamounah, Fadhil S.,Lee, Ji-Woong
(2020/10/30)

Multicomponent Synthesis of Sulfones and Sulfides from Triarylbismuthines and Sodium Metabisulfite in Deep Eutectic Solvents
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.
supporting information
p. 3462 - 3467
(2020/06/04)

Diaryl disulfides and thiosulfonates as combretastatin A-4 analogues: Synthesis, cytotoxicity and antitubulin activity
Diaryl disulfides and diaryl thiosulfonates were synthesized with the two phenyl rings of all compounds bearing identical halide substituents. Because of structural similarity to the potent antimitotic natural product combretastatin A-4 (CA-4), the compounds were examined for inhibition of tubulin polymerization, and the thiosulfonates were more active than the disulfides. The nine thiosulfonates had IC50 values ranging from 1.2 to 9.1 μM, as compared with 1.3 μM obtained with CA-4. The compounds thus ranged from equipotent with CA-4 to 7-fold less active. The nine disulfides had IC50 values ranging from 1.2 to 5.1 μM, as compared with 0.54 μM obtained with CA-4. The compounds thus ranged from less than half as active as CA-4 to over 9-fold less active. The most active members of each group, 2 g and 3c, in the assembly assay were modeled into the colchicine site. Compound 3c had significant hydrophobic interactions with β-tubulin residues CYS 241 and ALA 250, and its thiosulfonate bridge made a hydrogen bond with β-tubulin residue ASN 258. Compound 2 g had hydrophobic interactions with β-tubulin residues ALA 250, CYS 241 and ALA 254, but there was no significant interaction of the disulfide bridge with tubulin.
Bai, Ruoli,Barbosa, Euzébio Guimar?es,Beatriz, Adilson,Hamel, Ernest,Khodyuk, Rejane Gon?alves Diniz,Louren?o, Estela Mariana Guimar?es,de Lima, Dênis Pires,dos Santos, Edson dos Anjos
(2020/07/07)

Method for pipeline continuous production of aryl disulfide ether compounds
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)

Preparation method for symmetric diaryl disulfide
The invention discloses a preparation method for symmetric diaryl disulfide. The preparation method comprises the following steps: using aromatic hydrocarbon as shown in a general formula (I) as a rawmaterial and reacting with chlorosulfonic acid to generate aryl chlorosulfonic acid, and reacting with sulfoxide chloride to synthesize aryl sulfonyl chloride as shown in a general formula (II); andpreparing the symmetric diaryl disulfide as shown in a general formula (III) under the action of a reducing agent through a reduction reaction by the aryl sulfonyl chloride as shown in the general formula (II). The disclosed preparation method for the symmetric diaryl disulfide has many advantages of low toxicity of the reaction raw material, short reaction time, cheap reagents and easy acquisition, convenient separation and purification and the like, and has very high application value and industrial production value.
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Paragraph 0048; 0049; 0050; 0052

(2019/04/17)

Cyclic telluride reagents with remarkable glutathione peroxidase-like activity for purification-free synthesis of highly pure organodisulfides
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
p. 3647 - 3655
(2019/07/22)

T BuOK-triggered bond formation reactions
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
p. 24025 - 24029
(2019/08/13)

Biocatalytic synthesis of diaryl disulphides and their bio-evaluation as potent inhibitors of drug-resistant Staphylococcus aureus
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
p. 171 - 178
(2019/01/04)

Making the SF5 Group More Accessible: A Gas-Reagent-Free Approach to Aryl Tetrafluoro-λ6-sulfanyl Chlorides
Modern pentafluorosulfanyl (SF5) chemistry has an Achilles heel: synthetic accessibility. Herein, we present the first approach to aryl-SF4Cl compounds (key intermediates in state-of-the-art aryl-SF5 synthesis) that overco
Pitts, Cody Ross,Bornemann, Dustin,Liebing, Phil,Santschi, Nico,Togni, Antonio
supporting information
p. 1950 - 1954
(2019/01/25)

Visible-light-induced metal and reagent-free oxidative coupling of: Sp 2 C-H bonds with organo-dichalcogenides: Synthesis of 3-organochalcogenyl indoles
Here, a unique visible-light-induced method for the organochalcogenation of the sp2 C-H bonds of indoles and aniline has been presented using diaryl dichalcogenides (S, Se, and Te) and oxygen as an oxidant avoiding a photocatalyst, base, catalyst, and reagent in acetone at room temperature. This benign protocol allows one to access a wide range of 3-arylselenylindoles, 3-arylthioindoles and even 3-aryltelluroindoles with good to excellent yields. Various functionalities namely, methoxy, and halo either on indoles or aryl dichalcogenides showed amenability to the developed reaction. Furthermore, thiocyanation of the sp2 C-H bonds of indoles has been accomplished by this visible light induced method. A mechanistic understanding by UV-visible, EPR spectroscopy, and cyclic voltammetry suggests that light induces electron transfer from the electron rich arene to oxygen providing an arene radical cation and a superoxide radical anion. Subsequently, reaction of the radical cation with aryl dichalcogenides provides a diaryl chalcogenyl cation which upon removal of protons gave unsymmetrical 3-indolyl aryl chalcogenides.
Rathore, Vandana,Kumar, Sangit
supporting information
p. 2670 - 2676
(2019/06/03)

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
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
supporting information
p. 72 - 77
(2019/05/15)

Synthesis and nano-Pd catalyzed chemoselective oxidation of symmetrical and unsymmetrical sulfides
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
p. 3048 - 3055
(2019/03/21)

PTAB mediated open air synthesis of sulfonamides, thiosulfonates and symmetrical disulfanes
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
p. 2360 - 2364
(2018/05/24)

Base-controlled Fe(Pc)-catalyzed aerobic oxidation of thiols for the synthesis of S-S and S-P(O) bonds
Fe(Pc)-Catalyzed aerobic oxidation of thiols for the synthesis of disulfides has been developed under mild reaction conditions. In addition, an aerobic oxidative cross-dehydrogenative coupling (CDC) reaction of thiols with P(O)-H compounds (H-phosphonates and H-phosphine oxide) for the formation of S-P(O) bonds has been demonstrated under the Fe(Pc) catalysis system with a base additive. Control experiments revealed that the use of a base (DIPA) in this system controls the synthetic pathways in which thiophosphates are formed.
Huang, Hai,Ash, Jeffrey,Kang, Jun Yong
p. 4236 - 4242
(2018/06/21)

Synthesis and characterization of sulfamic acid supported on Fe3O4 nanoparticles: A green, versatile and magnetically separable acidic catalyst for oxidation reactions and Knoevenagel condensation
Sulfamic acid immobilized on diethylenetriamine functionalized Fe3O4 nanoparticles (SA-DETA-Fe3O4) was successfully prepared and characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), vibrating sample magnetometer (VSM), thermo gravimetric analysis (TGA), X-Ray diffraction (XRD) and scanning electron microscopy (SEM). The sulfamic acid was found as a magnetically separable and highly active catalyst for the oxidative coupling thiols, oxidation of sulfides. Furthermore, the SA-DETA-Fe3O4 showed the high catalytic activity in Knoevenagel condensation of aromatic aldehydes with active methylene compounds (malononitrile and ethyl cynoacetate). The nanosolid catalyst could be easily recovered by a simple magnetic separation and reused for many cycles without deterioration in catalytic activity.
Shiri, Lotfi,Narimani, Hojatollah,Kazemi, Mosstafa
(2017/10/06)

Laccase-catalyzed in situ generation and regeneration of N-phenyltriazolinedione for the aerobic oxidative homo-coupling of thiols to disulfides
The first report on aerobic in situ generation and regeneration of N-phenyltriazolinedione, a valuable oxidizing agent, from a catalytic amount of N-phenyl urazole in the presence of a laccase enzyme is presented. The application of a 4-phenyl urazole/Laccase/O2 as a new cooperative catalytic oxidation system is reported for a transition-metal-free and halogen free oxidative homo-coupling reaction of structurally diverse thiols to their corresponding disulfides with good to excellent yields in a phosphate buffer solution under mild reaction conditions.
Khaledian, Donya,Rostami, Amin,Zarei, Seyed Amir
p. 75 - 78
(2018/06/26)

Photo-induced thiol coupling and C-H activation using nanocrystalline lead-halide perovskite catalysts
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
p. 4257 - 4263
(2018/08/24)

An Organodiselenide with Dual Mimic Function of Sulfhydryl Oxidases and Glutathione Peroxidases: Aerial Oxidation of Organothiols to Organodisulfides
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
supporting information
p. 6274 - 6278
(2018/10/05)

A One-Pot Cascade Reaction by Combining NH-Sulfoximines with Thiophenols Under Mild Conditions
A general protocol for the N-thioetherification of NH-sulfoximines has been developed. Catalyzed by [Cu(DMAP)4I]I, N-sulfenyl sulfoximines were synthesized by a one-pot cascade reaction with commercially available thiophenols as the sulfur sour
Peng, Yao,Lin, Yan,Nie, Ruifang,Zheng, Yang,Liu, Yanzhao,Guo, Li,Wu, Yong
p. 844 - 850
(2018/02/21)

Stereoretentive C(sp3)-S Cross-Coupling
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.
supporting information
p. 18140 - 18150
(2019/01/04)

Stabilized and reactive fluorinated phthalocyanine-functionalized solid-state support composites
A new class of organic-inorganic hybrid composite materials, composites of a fluoroalkyl fluorophthalocyanine and a solid-state support containing an imidazole group. The new class of composite materials can be used as a heterogeneous catalyst for the het
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(2018/05/16)

Visible-Light Photocatalytic Synthesis of Amines from Imines via Transfer Hydrogenation Using Quantum Dots as Catalysts
CdSe/CdS core/shell quantum dots (QDs) can be used as stable and highly active photoredox catalysts for efficient transfer hydrogenation of imines to amines with thiophenol as a hydrogen atom donor. This reaction proceeds via a proton-coupled electron transfer (PCET) from the QDs conduction band to the protonated imine followed by hydrogen atom transfer from the thiophenol to the α-aminoalkyl radical. This precious metal free transformation is easy to scale up and can be carried out by a one-pot protocol directly from aldehyde, amine, and thiophenol. Additional advantageous features of this protocol include a wide substrate scope, high yield of the amine products, extremely low catalyst loading (0.001 mol %), high turnover number (105), and the mild reaction conditions of using visible light or sun light at room temperature in neutral media.
Xi, Zi-Wei,Yang, Lei,Wang, Dan-Yan,Pu, Chao-Dan,Shen, Yong-Miao,Wu, Chuan-De,Peng, Xiao-Gang
supporting information
p. 11886 - 11895
(2018/09/25)

A novel dual-nano assisted synthesis of symmetrical disulfides from aryl/alkyl halides
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
supporting information
p. 1927 - 1938
(2018/07/21)

18F-Fluoroform: A 18F-trifluoromethylating agent for the synthesis of SCF218F-aromatic derivatives
Herein the synthesis of various SCF218F-containing derivatives is reported by a transition metal-free process. By using HCF218F, readily generated from a bench-stable difluoromethyl sulfonium salt, various aromatic disulfides were easily converted into the desired radiolabelled trifluoromethylthiolated compounds in the presence of a base. This protocol allowed the formation of the SCF218F-containing aromatic derivatives in good to excellent radiochemical yields. This process was also extended to the corresponding selenium derivative.
Carbonnel, Elodie,Besset, Tatiana,Poisson, Thomas,Labar, Daniel,Pannecoucke, Xavier,Jubault, Philippe
supporting information
p. 5706 - 5709
(2017/07/10)

Cu(II) immobilized on Fe3O4–diethylenetriamine: A new magnetically recoverable catalyst for the synthesis of 2,3-dihydroquinazolin-4(1H)-ones and oxidative coupling of thiols
Cu(II) immobilized on Fe3O4–diethylenetriamine was designed as a new, inexpensive and efficient heterogeneous catalyst for the synthesis of 2,3-dihydroquinazolin-4(1H)-ones and the oxidative coupling of thiols. The structure of the nanomagnetic catalyst was comprehensively characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, vibrating sample magnetometry, thermogravimetric analysis, X-ray diffraction and atomic absorption spectroscopy. Simple preparation of the catalyst from commercially available materials, high catalytic activity, simple operation, high yields, use of green solvents, easy magnetic separation and reusability of the catalyst with unaltered activity make our protocol a green and feasible synthetic strategy.
Shiri, Lotfi,Ghorbani-Choghamarani, Arash,Kazemi, Mosstafa
(2017/04/21)

Fe3O4 MNPs-DETA/Benzyl-Br3: A new magnetically reusable catalyst for the oxidative coupling of thiols
We report a new strategy to immobilize a bromine source on the surface of magnetic Fe3O4 nanoparticles (Fe3O4 MNPs-DETA/Benzyl-Br3) leading to amagnetically recoverable catalyst, which exhibits high catalytic efficiency in oxidative coupling of thiols to the disulfides (89–98%). The Fe3O4 MNPs-DETA/Benzyl-Br3 catalyst was fabricated by anchoring 3-chloropropyltrimethoxysilane (CPTMS) onmagnetic Fe3O4 nanoparticles, followed with N-benzylation and reaction with bromine in tetrachloridecarbon. The resulting nanocomposite was analyzed by a series of characterization techniques such as FT-IR, SEM, TGA, VSM and XRD. The catalyst could be recovered viamagnetic attraction and could be recycled at least 5 times without appreciable decrease in activity.
Shiri, Lotfi,Kazemi, Mosstafa
p. 1171 - 1176
(2017/09/27)

Synthesis and characterization of tribenzyl ammonium-tribromide supported on magnetic Fe3O4 nanoparticles: a robust magnetically recoverable catalyst for the oxidative coupling of thiols and oxidation of sulfides
Abstract: Taking into account the principles of green chemistry, magnetic nanoparticles, especially Fe3O4 nanoparticles, open up a new chapter in modern organic synthesis to inset a fascinating, stupendous and efficient catalytic strategy for facilitating catalyst recovery in various chemical reactions. Inspired by this topic, tribenzyl ammonium-tribromide immobilized on magnetic nanoparticles (Fe3O4–TBA-Br3) as a bromine source was successfully synthesized and its catalytic activity in the oxidative coupling of thiols and oxidation of sulfides was investigated. It is the first report on the use of the immobilized bromine source on Fe3O4 nanoparticles as a nanomagnetic recyclable catalyst for the oxidative coupling of thiols. The nanosolid catalyst could be easily recovered by a simple magnetic separation and reused for several cycles without significant degradation in catalytic activity. Graphical Abstract: [Figure not available: see fulltext.]
Shiri, Lotfi,Ghorbani-Choghamarani, Arash,Kazemi, Mosstafa
p. 2707 - 2724
(2017/04/18)

Thieme Chemistry Journals Awardees - Where Are They Now?Molybdenum(V)-Mediated Synthesis of Nonsymmetric Diaryl and Aryl Alkyl Chalcogenides
Oxidative chalcogenation reaction using molybdenum(V) reagents provides fast access to a wide range of nonsymmetric aryl sulfides and selenides. The established protocol is tolerated by a variety of labile functions, protecting groups, and aromatic heterocycles. In particular, when labile moieties are present, the use of molybdenum(V) reagents provides superior yields compared to other oxidants.
Franzmann, Peter,Beil, Sebastian B.,Winterscheid, Peter M.,Schollmeyer, Dieter,Waldvogel, Siegfried R.
supporting information
p. 957 - 961
(2017/05/05)

Regiocontrolled direct C4 and C2-methyl thiolation of indoles under rhodium-catalyzed mild conditions
A straightforward Rh(iii)-catalyzed general strategy was developed for the site-selective remote C4 (sp2) and C2 (sp3)-methyl thiolation of an indole core, keeping the oxime directing group at the C3 position. The transformation was accomplished under mild conditions with a wide scope and functional group tolerance. The directing group can easily be removed after operation. Methyl substitution at the C2 position of the indole core led to C2 (sp3)-methyl thiolation.
Maity, Saurabh,Karmakar, Ujjwal,Samanta, Rajarshi
supporting information
p. 12197 - 12200
(2017/11/16)

Tunable and Practical Synthesis of Thiosulfonates and Disulfides from Sulfonyl Chlorides in the Presence of Tetrabutylammonium Iodide
A tunable and practical synthesis of electrophilic sulfenylating reagents, thiosulfonates and disulfides, from inexpensive and easily available sulfonyl chlorides, has been developed. By appropriate choice of solvents, the reaction of sulfonyl chlorides and tetrabutylammonium iodide gave the target products in good to excellent yields, respectively. These transformations probably proceed through a reducing–coupling pathway. (Figure presented.).
Zheng, Yong,Qing, Feng-Ling,Huang, Yangen,Xu, Xiu-Hua
supporting information
p. 3477 - 3481
(2016/11/13)

Polyoxometalate Cluster-Incorporated Metal-Organic Framework Hierarchical Nanotubes
A one-pot solvothermal strategy was designed to synthesize two kinds of bi-metallic hierarchical Fe/Co-BTC nanotubes modulated by Keggin-type POMs. Iron(iii) acetylacetonate and cobalt(iii) acetylacetonate were dissolved in a dimethylformamide (DMF)/decanol mixture. Then NaPW12, 3.0 mL of water and 0.35 mL of 1,3,5-benzenetricarboxylic acid solution were added successively into the DMF/decanol solution. After stirring for several minutes, the starting solution was transferred into a 40-mL Teflon-lined stainless-steel autoclave. The sealed vessel was then heated at 100°C for 3 h before it was cooled down to room temperature. The electrochemical performance of the as-prepared products were measured using a two electrode cell. It was found that Tube1 exhibited higher catalytic properties than either MOF1 or P1 . In other words, the properties of the composite were better than those of the individual components, thus confirming the synergistic effect of the composite. Interestingly, the activity of Tube2 was almost the same as that of T1 , which may be attributed to its high specific surface area.
Xu, Xiaobin,Chen, Shuangming,Chen, Yifeng,Sun, Hongyu,Song, Li,He, Wei,Wang, Xun
p. 2982 - 2990
(2016/06/14)

An efficient and convenient method for the preparation of disulfides from thiols using oxygen as oxidant catalyzed by tert-butyl nitrite
An efficient and convenient tert-butyl nitrite-catalyzed selective aerobic oxidation of thiols has been developed. Under the optimal reaction conditions, a number of thiol derivatives including aromatic thiols, heteroaromatic thiols and aliphatic thiols can be converted into their corresponding disulfides in good to excellent yields.
Yi, Shan-Li,Li, Mei-Chao,Hu, Xin-Quan,Mo, Wei-Min,Shen, Zhen-Lu
p. 1505 - 1508
(2016/09/23)

Visible-light-mediated facile synthesis of disulfides using reusable TiO2/MoS2nanocomposite photocatalyst
A nontoxic and inexpensive TiO2/MoS2nanocomposite was prepared and employed as an efficient photocatalyst for the synthesis of symmetrical disulfides under visible light irradiation at room temperature. Both aryl and alkyl thiols survived the reaction conditions, affording the corresponding disulfides in good to excellent yields. The photocatalyst could be easily recovered by simple centrifugation and filtration and reused several times without significant loss in its activity.
Liu, Wenjie,Wang, Cancan,Huang, Yibo,Chen, Qun,Wang, Liang,He, Mingyang
supporting information
p. 1268 - 1274
(2016/08/16)