1141-88-4Relevant articles and documents
Accessing Ni(III)-thiolate versus Ni(II)-thiyl bonding in a family of Ni-N2S2 synthetic models of NiSOD
Broering, Ellen P.,Dillon, Stephanie,Gale, Eric M.,Steiner, Ramsey A.,Telser, Joshua,Brunold, Thomas C.,Harrop, Todd C.
, p. 3815 - 3828 (2015)
Superoxide dismutase (SOD) catalyzes the disproportionation of superoxide (O2?-) into H2O2 and O2(g) by toggling through different oxidation states of a first-row transition metal ion at its active site. Ni-containing SODs (NiSODs) are a distinct class of this family of metalloenzymes due to the unusual coordination sphere that is comprised of mixed N/S-ligands from peptide-N and cysteine-S donor atoms. A central goal of our research is to understand the factors that govern reactive oxygen species (ROS) stability of the Ni-S(Cys) bond in NiSOD utilizing a synthetic model approach. In light of the reactivity of metal-coordinated thiolates to ROS, several hypotheses have been proffered and include the coordination of His1-Nδ to the Ni(II) and Ni(III) forms of NiSOD, as well as hydrogen bonding or full protonation of a coordinated S(Cys). In this work, we present NiSOD analogues of the general formula [Ni(N2S)(SR′)]-, providing a variable location (SR′ = aryl thiolate) in the N2S2 basal plane coordination sphere where we have introduced o-amino and/or electron-withdrawing groups to intercept an oxidized Ni species. The synthesis, structure, and properties of the NiSOD model complexes (Et4N)[Ni(nmp)(SPh-o-NH2)] (2), (Et4N)[Ni(nmp)(SPh-o-NH2-p-CF3)] (3), (Et4N)[Ni(nmp)(SPh-p-NH2)] (4), and (Et4N)[Ni(nmp)(SPh-p-CF3)] (5) (nmp2- = dianion of N-(2-mercaptoethyl)picolinamide) are reported. NiSOD model complexes with amino groups positioned ortho to the aryl-S in SR′ (2 and 3) afford oxidized species (2ox and 3ox) that are best described as a resonance hybrid between Ni(III)-SR and Ni(II)-?SR based on ultraviolet-visible (UV-vis), magnetic circular dichroism (MCD), and electron paramagnetic resonance (EPR) spectroscopies, as well as density functional theory (DFT) calculations. The results presented here, demonstrating the high percentage of S(3p) character in the highest occupied molecular orbital (HOMO) of the four-coordinate reduced form of NiSOD (NiSODred), suggest that the transition from NiSODred to the five-coordinate oxidized form of NiSOD (NiSODox) may go through a four-coordinate Ni-?S(Cys) (NiSODox-Hisoff) that is stabilized by coordination to Ni(II).
3,6-Di(pyridin-2-yl)-1,2,4,5-tetrazine (pytz) mediated metal-free mild oxidation of thiols to disulfides in aqueous medium
Samanta, Suvendu,Ray, Shounak,Ghosh, Abhisek Brata,Biswas, Papu
, p. 39356 - 39363 (2016)
Thiols are efficiently oxidized to disulfides (RSSR) in the presence of 3,6-di(pyridin-2-yl)-1,2,4,5-tetrazine (pytz) in aqueous medium, as well as in the absence of a solvent under mild and metal-free conditions. A broad range of alkyl, aryl and heterocyclic symmetrical disulfides can be easily obtained in almost quantitative yields. The X-ray single crystal structure of 2-aminocyclopent-1-ene-1-carbothioic dithioperoxyanhydride (disulfide obtained from 2-aminocyclopentene-1-dithiocarboxylic acid, ACDA) is reported. The reaction mechanism has been studied thoroughly. It is shown that the reaction proceeds through the formation of an organosulphur radical. Pytz interacts with thiol to accept one electron and produces an organosulphur radical. Pytz ultimately accepts two electrons to form H2pytz and is capable of oxidizing 2 equivalents of thiols.
Bovine serum albumin triggered waste-free aerobic oxidative coupling of thiols into disulphides on water: An extended synthesis of bioactive dithiobis(phenylene)bis(benzylideneimine) via sequential oxidative coupling-condensation reactions in one pot from aminothiophenol and benzaldehyde
Saima,Lavekar, Aditya G.,Kumar, Rajesh,Sinha, Arun K.
, p. 113 - 123 (2015)
Bovine serum albumin (BSA) has been explored for aerobic oxidative coupling of thiols (aromatic, heterocyclic as well as aliphatic) "on water" towards formation of disulphides (SS) without using any metal/non-metal complexes, bases and additives, which renders the process environmentally benign and economically attractive with good recyclability (up to four cycles). The developed green protocol was further extended for synthesis of diallyldisulphide (DADS), an important constituent of natural occurring allicin. Among various synthesized disulphides, bis(2-aminophenyl)disulphide, obtained by oxidative coupling of 2-aminothiophenol in BSA, was further utilized for condensation with benzaldehyde in the same pot thus enabling easy access to bioactive dithiobis(phenylene)bis(benzyldeneimine). This is the first example of BSA catalysed sequential (oxidation/condensation) reaction where one SS and two CN bonds are formed solely "on water."
A comparative study of oxidants on thiols
Ramadas,Srinivasan,Janarthanan,Pritha
, p. 352 - 354 (1996)
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Sodium Tellurite as a Mild and Selective Oxidizing Agent for Thiols: Its Use in the One-Pot Synthesis of Unsymmetrical Disulfides
Suzuki, Hitomi,Kawato, Sei-ichi,Nasu, Akira
, p. 626 - 627 (1992)
Sodium tellurite acts as a mild and highly selective oxidizing agent for thiols under phase-transfer conditions at room temperature.Aromatic and benzylic thiols are rapidly converted to disulfides.Short-chain primary thiols undergo oxidation in preference to long-chain thiols.Secondary thiols are sluggish in oxidation and tertiary thiols remain intact.No overoxidation of the sulfur atom is observed.Similar results are also obtained with sodium tellurate.
Facile Synthesis of Benzo[ d ]azol-2(3 H)-ones Using 2-Phenoxycarbonyl-4,5-dichloropyridazin-3(2 H)-one as Green CO Source
Ryu, Ki Eun,Kim, Bo Ram,Sung, Gi Hyeon,Yoon, Hyo Jae,Yoon, Yong-Jin
, p. 1985 - 1990 (2015)
Developing eco-friendly, stable, and easy-to-handle acyl sources is of great importance in synthetic and green chemistry. This study describes the synthesis of benzo[d]azol-2(3H)-ones such as benzo[d]thiazol-2(3H)-ones, benzo[d]oxazol-2(3H)-ones, and benzo[d]imidazol-2(3H)-ones using 2-phenoxycarbonyl-4,5-dichloropyridazin-3(2H)-one in one pot. The reaction reported is carried out under neutral or acidic conditions in the presence of zinc or sodium bicarbonate to give the corresponding heterocycles in good to excellent yields. The reaction uses a solid stable carbonyl source that is a recyclable functional-group carrier, pyridazin-3(2H)-one.
Preparation of benzothiazolyl-decorated nanoliposomes
Mourtas, Spyridon,Christodoulou, Panayiota,Klepetsanis, Pavlos,Gatos, Dimitrios,Barlos, Kleomenis,Antimisiaris, Sophia G.
, (2019)
Amyloid β (Aβ) species are considered as potential targets for the development of diagnostics/therapeutics towards Alzheimer’s disease (AD). Nanoliposomes which are decorated with molecules having high affinity for Aβ species may be considered as potential carriers for AD theragnostics. Herein, benzothiazolyl (BTH) decorated nanoliposomes were prepared for the first time, after synthesis of a lipidic BTH derivative (lipid-BTH). The synthetic pathway included acylation of bis(2-aminophenyl) disulfide with palmitic acid or palmitoyl chloride and subsequent reduction of the oxidized dithiol derivative. The liberated thiols were able to cyclize to the corresponding benzothiazolyl derivatives only after acidification of the reaction mixture. Each step of the procedure was monitored by HPLC analysis in order to identify all the important parameters for the formation of the BTH-group. Finally, the optimal methodology was identified, and was applied for the synthesis of the lipid-BTH derivative. BTH-decorated nanoliposomes were then prepared and characterized for physicochemical properties (size distribution, surface charge, physical stability, and membrane integrity during incubation in presence of buffer and plasma proteins). Pegylated BTH-nanoliposomes were demonstrated to have high integrity in the presence of proteins (in comparison to non-peglated ones) justifying their further exploitation as potential theragnostic systems for AD.
1,2,4,3,5-benzotrithiadiazepine and its unexpected hydrolysis to unusual 7H,14H-dibenzo[d,i][1,2,6,7,3,8]tetrathiadiazecine
Makarov,Shakirov,Shuvaev,Bagryanskaya,Gatilov,Zibarev
, p. 1774 - 1775 (2001)
Previously unknown 1,2,4,3,5-benzotrithiadiazepine 1 was prepared by 1:1 condensation of Ph-N=S=N-SiMe3 with S2Cl2 followed by intramolecular ortho-cyclization of [Ph-N=S=N-S-S-Cl] intermediate, and hydrolyzed in pyridine
Synthesis of 2-arylbenzothiazoles via direct condensation between in situ generated 2-aminothiophenol from disulfide cleavage and carboxylic acids
Coelho, Felipe L.,Campo, Leandra F.
, p. 2330 - 2333 (2017)
In this work we describe a simple and efficient general methodology for 2-arylbenzothiazole preparation employing disulfides and carboxylic acids. The reaction is promoted by tributylphosphine that acts both in disulfide bond cleavage and as activating agent for coupling with carboxylic acids. The reaction scope was studied using bis(2-aminophenyl)disulfide and different carboxylic acids with donor/withdrawing substituents, which resulted in the desired 2-arylbenzothiazole with moderate to good yields. The method was tested with success in preparation of the amyloid probe 2-(4-aminophenyl)-6-methoxybenzothiazole that employed a substituted bis(2-aminophenyl)disulfide.
Ball-milling synthesized hydrotalcite supported Cu-Mn mixed oxide under solvent-free conditions: An active catalyst for aerobic oxidative synthesis of 2-acylbenzothiazoles and quinoxalines
Meng, Xu,Bi, Xiuru,Yu, Chaoying,Chen, Gexin,Chen, Baohua,Jing, Zhenqiang,Zhao, Peiqing
, p. 4638 - 4644 (2018)
A rapid solvent-free ball-milling method was developed to prepare a hydrophobic hydrotalcite supported Cu-Mn mixed oxide catalyst (Cu-Mn/HT). The mechanochemically prepared catalyst exhibited high catalytic activity and recyclability towards the aerobic synthesis of 2-acylbenzothiazoles and quinoxalines in green medium ethanol compared with the ones synthesized via grinding and wet-impregnation. Moreover, control experiments showed that the catalyst was successfully used in green oxidative esterification and coupling as well. Cu-Mn/HT was characterized by BET, ICP, XRD, XPS, SEM and TEM, which indicated that more surface oxygen vacancies and formed CuMn2O4 species on HT might contribute to the catalytic activity.
Silica-supported bis (trimethylsilyl) chromate: Oxidation of thiols to their corresponding disulfides
Heravi, Majid M.,Derikvand, Fatemeh,Oskooie, Hossein A.,Shoar, Rahim Hekmat,Tajbakhsh, Mahmood
, p. 513 - 517 (2007)
An efficient and convenient method for the oxidation of thiols mediated by silica-supported bis (trimethylsilyl) chromate (BTSC) in acetonitrile is reported. Copyright Taylor & Francis Group, LLC.
Copper(II)-catalyzed disulfide scission-stepwise aerobic oxidative cleavage to sulfinate and sulfonate and reductive anaerobic cleavage to thiols
Lumb, Isha,Hundal, Maninder Singh,Hundal, Geeta
, p. 7770 - 7779 (2014)
The Cu(II)-catalyzed oxidative and reductive cleavage of the disulfide bond of N-(2-(2-(2-picolinamido)phenyl)disulfanyl)phenyl)picolinamide, L, is reported for the first time. Aerobic oxidation with Cu(II) gives complete oxidation of S-S bond to sulfonat
Clay catalysis: Condensation of orthoesters with O-substituted aminoaromatics into heterocycles
Villemin, Didier,Hammadi, Mohamed,Martin, Benoit
, p. 2895 - 2899 (1996)
KSF clay catalysed the condensation of orthoesters with o-substituted aminoaromatics into heterocycles in toluene under reflux or without solvent under microwave irradiation.
Structures, Spectroscopic Properties, and Dioxygen Reactivity of 5- and 6-Coordinate Nonheme Iron(II) Complexes: A Combined Enzyme/Model Study of Thiol Dioxygenases
Gordon, Jesse B.,McGale, Jeremy P.,Prendergast, Joshua R.,Shirani-Sarmazeh, Zahra,Siegler, Maxime A.,Jameson, Guy N. L.,Goldberg, David P.
, p. 14807 - 14822 (2018)
The synthesis of four new FeII(N4S(thiolate)) complexes as models of the thiol dioxygenases are described. They are composed of derivatives of the neutral, tridentate ligand triazacyclononane (R3TACN; R = Me, iPr) and 2-aminobenzenethiolate (abtx X = H, CF3), a non-native substrate for thiol dioxygenases. The coordination number of these complexes depends on the identity of the TACN derivative, giving 6-coordinate (6-coord) complexes for FeII(Me3TACN)(abtx)(OTf) (1: X = H; 2: X = CF3) and 5-coordinate (5-coord) complexes for [FeII(iPr3TACN)(abtx)](OTf) (3: X = H; 4: X = CF3). Complexes 1-4 were examined by UV-vis, 1H/19F NMR, and M?ssbauer spectroscopies, and density functional theory (DFT) calculations were employed to support the data. M?ssbauer spectroscopy reveals that the 6-coord 1-2 and 5-coord 3- 4 exhibit distinct spectra, and these data are compared with that for cysteine-bound CDO, helping to clarify the coordination environment of the cys-bound FeII active site. Reaction of 1 or 2 with O2 at -95 °C leads to S-oxygenation of the abt ligand, and in the case of 2, a rare di(sulfinato)-bridged complex, [Fe2III(μ-O)((2-NH2)p-CF3C6H3SO2)2](OTf)2 (5), was obtained. Parallel enzymatic studies on the CDO variant C93G were carried out with the abt substrate and show that reaction with O2 leads to disulfide formation, as opposed to S-oxygenation. The combined model and enzyme studies show that the thiol dioxygenases can operate via a 6-coord FeII center, in contrast to the accepted mechanism for nonheme iron dioxygenases, and that proper substrate chelation to Fe appears to be critical for S-oxygenation.
Braithwaite et al.
, p. 5,7 (1975)
Metalloclayzymes: An efficient oxidative coupling of thiols catalysed by FE (III) montmorillonite in buffer
Meshram,Kache, Rajashaker
, p. 2403 - 2406 (1997)
An effcient S-S bond formation is described in buffer solution (pH 7.2) catalysed by Fe(III) ion exchanged montmorillonite.
The rearrangement of trifluoroacetylchromenes to trifluoromethylchromenols
Osyanin, Vitaly A.,Popova, Yulia V.,Sakhnenko, Darina V.,Osipov, Dmitry V.,Klimochkin, Yuri N.
, p. 559 - 563 (2016)
[Figure not available: see fulltext.] The reaction of o-phenylenediamine with condensed 4H-pyrans containing a trifluoroacetyl group at the β-position relative to the oxygen atom led to 2-(trifluoromethyl)chroman-2-ols and 3-(trifluoromethyl)-2,3-dihydro-1H-benzo[f]chromen-3-ols via a cascade process that was initiated by a Michael reaction.
Synthesis and Characterization of Disulfide-Schiff Base Derivatives and in vitro Investigation of Their Antibacterial Activity Against Multidrug-Resistant Acinetobacter baumannii Isolates: A New Study
Durmus,Dalmaz,Cal?skan,Dulger
, p. 305 - 311 (2018)
In this study two different methods without a catalyst and with a CeO2 nano catalyst were used for the synthesis of dimeric disulfide-Schiff bases. The dimeric disulfide-Schiff base derivatives were characterized by FT-IR, NMR, and MS spectra, and elemental analysis. The disulfide-Schiff bases and their derivatives 2–5c were screened for in vitro antibacterial activity against 40 multidrug-resistant strains of Acinetobacter baumannii, and their minimum inhibitory concentrations were determined. Most of products exhibited high antibacterial activity against Acinetobacter baumannii.
Synthesis and Characterization of Magnetic Functionalized Ni and Cu Nano Catalysts and Their Application in Oxidation, Oxidative Coupling and Various Multi-Component Reactions
Hajjami, Maryam,Sheikhaei, Shiva,Gholamian, Fatemeh,Yousofvand, Zakieh
, p. 2420 - 2435 (2021/01/04)
Abstract: Two magnetic nano catalysts of nickel and copper, Fe3O4@SiO2@DOP-BenPyr-M(II), (M=Ni and Cu) have been synthesized. These catalysts were applied as recoverable, efficient and new heterogeneous catalysts for the high yielding and room temperature one-pot procedure of selective oxidation of sulfides to sulfoxides and oxidative coupling of thiols to disulfides. In addition, the catalytic activity of Fe3O4@SiO2@DOP-BenPyr-Ni(II) was investigated as heterogeneous nanocatalyst for synthesis of 2,3-dihydroquinazolin-4(1H)-ones, 5-substituted 1H-tetrazoles and polyhydroquinolines. The synthesized catalysts were characterized by FT-IR, TGA, XRD, VSM, EDX, ICP and SEM techniques. These catalysts were recovered by an external magnet and reused several times without significant loss of catalytic efficiency. Graphic Abstract: [Figure not available: see fulltext.]
Synthesis and biological evaluation of disulfides as anticancer agents with thioredoxin inhibition
Wei, Xiangxu,Zhong, Miao,Wang, Song,Li, Lexun,Song, Zi-Long,Zhang, Junmin,Xu, Jianqiang,Fang, Jianguo
, (2021/03/24)
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.
