- Acyl Derivatives of Eudesmanolides To Boost their Bioactivity: An Explanation of Behavior in the Cell Membrane Using a Molecular Dynamics Approach
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Semisynthetic analogs of natural products provide an important approach to obtain safer and more active drugs and they can also have enhanced physicochemical properties such as persistence, cross-membrane processes and bioactivity. Acyl derivatives of different natural product families, from sesquiterpene lactones to benzoxazinoids, have been synthesized and tested in our laboratories. These compounds were evaluated against tumoral and nontumoral cell lines to identify selective derivatives with a reduced negative impact upon application. The mode of action of these compounds was analyzed by anti-caspase-3 assays and molecular dynamics simulations with cell membrane re-creation were also carried out. Aryl derivatives of eudesmanolide stand out from the other compounds and are better than current anticancer drugs such as etoposide in terms of selectivity and activity. Computational studies provide evidence that lipophilicity plays a key role and the 4-fluorobenzoyl derivative can pass easily through the cell membrane.
- Mejías, Francisco J. R.,Durán, Alexandra G.,Zorrilla, Jesús G.,Varela, Rosa M.,Molinillo, José M. G.,Valdivia, Manuel M.,Macías, Francisco A.
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p. 1297 - 1307
(2021/02/09)
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- Preparation method of symmetric disulfide bond-containing compound
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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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Paragraph 0020; 0045-0047
(2021/11/21)
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- Synthesis of phenoxathiins and phenothiazines by aryne reactions with thiosulfonates
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Novel synthetic methods for phenoxathiins and phenothiazines by aryne reactions are disclosed. We found that phenoxathiins were efficiently prepared by the reaction between aryne intermediates and S-(2-hydroxyaryl) 4-toluenethiosulfo-nates. A synthetic method for phenothiazines was also developed by the reaction of arynes with S-(2-aminoaryl) 4-toluenethiosulfonates.
- Hosoya, Takamitsu,Kanemoto, Kazuya,Sakata, Yuki,Yoshida, Suguru
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supporting information
p. 593 - 596
(2020/05/19)
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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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- 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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- A mild and efficient method for the conversion of aldehydes into nitriles and thiols into disulfides using an ionic liquid oxidant
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A simple, mild and high yielding method for the conversion of various aldehydes to nitriles has been developed using an ionic liquid reagent, hexamethylene bis(N-methylimidazolium) bis(dichloroiodate) (HMBMIBDCI), in combination with aqueous ammonia in CH3CN at room temperature. Moreover, the treatment of aromatic and aliphatic thiols with HMBMIBDCI resulted in the corresponding disulfides in solvent-free condition at room temperature.
- Hosseinzadeh, Rahman,Golchoubian, Hamid,Nouzarian, Mahboobe
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p. 4713 - 4725
(2015/06/30)
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- Aerobic oxidation of thioles to disulfides catalyzed by mixed-addenda vanadium (V) substituted heteropolyacids
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The oxidation of thiols to related disulfides using mixed-addenda heteropolyacids as catalyst under mild condition has been studied. This system provides an efficient, convenient, and practical method for the syntheses of symmetrical disulfides. In this w
- Rezvani, M. A.,Harutyunyan, R.,Heravi, Majid M.
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p. 1232 - 1236,5
(2020/09/02)
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- H5PV2Mo10O40 as an efficient catalyst for the oxidation of thiols to the corresponding disulfides using hydrogen peroxide as the oxidant
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The H5PV2Mo10O40 catalyzed the oxidation of thiols to their homodisulfides using hydrogen peroxide as the oxidant under mild conditions is reported. This system provides an efficient, convenient and practical me
- Shojaei, Abdollah Fallah,Rezvani, Mohamad Ali,Heravi, Majid
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experimental part
p. 955 - 963
(2012/04/04)
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- Modifiable sulfur tethers as directing groups for aromatic C-H acetoxylation reactions
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A designed new class of modifiable sulfur tethers for aromatic C-H bond functionalizations is presented. As a model, the palladium-catalyzed directed acetoxylation reaction was studied. The more challenging sulfoxide tethers were the most effective in this transformation, showing a broad functionality tolerance, high S oxido-redox stability and no catalyst poisoning. Preliminary mechanistic studies indicate that the higher reactivity and selectivity shown by the sulfoxide tethers vs. the corresponding sulfones can be attributed to an extra coordination of the sulfoxide S atom to the catalyst. The utility of the presented methodology to generate structurally interesting aromatic derivatives by a subsequent modification of the S-tether is also exemplified.
- Richter, Heinrich,Beckendorf, Stephan,Mancheno, Olga Garcia
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supporting information; experimental part
p. 295 - 302
(2011/04/16)
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- Efficient route for the preparation of benzyloxy-substituted benzenesulfonyl chlorides from mercaptophenols
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A consistently high-yielding route has been developed for the preparation of benzyloxybenzenesulfonyl chlorides from mercaptophenols. This route allows rapid preparation of intermediates for array chemistry.
- Jumeaux, Coline,Cooper, David G.,Brown, Bruce T.,Forbes, Ian T.,Garzya, Vincenzo
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scheme or table
p. 1805 - 1808
(2011/06/20)
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- VEGFR INHIBITORS CONTAINING A ZINC BINDING MOIETY
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The present invention relates to VEGFR inhibitors and their use in the treatment of cell proliferative diseases such as cancer. The said derivatives may further act as HDAC inhibitors.
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Page/Page column 58; 59
(2009/04/25)
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- Highly chemoselective methylation and esterification reactions with dimethyl carbonate in the presence of NaY faujasite. The case of mercaptophenols, mercaptobenzoic acids, and carboxylic acids bearing OH substituents
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In the presence of NaY faujasite, the reactions of dimethyl carbonate (DMC) with several ambident nucleophiles such as o- and p-mercaptophenols (1a,b), o- and p-mercaptobenzoic acids (2a,b), o- and p-hydroxybenzoic acids (3a,b), mandelic and phenyllactic acids (4, 5), have been explored under batch conditions. Highly chemoselective reactions can be performed: at 150 °C, compounds 1 and 2 undergo only a S-methylation reaction, without affecting OH and CO2H groups; at 165 °C, acids 3-5 form the corresponding methyl esters, while both their aromatic and aliphatic OH substituents are fully preserved from methylation and/or transesterification processes. Typical selectivities are of 90-98% and isolated yields of products (S-methyl derivatives and methyl esters, respectively) are in the range of 85-96%. A comparative study with K2CO3 as a catalyst is also reported. Although the base (K2CO3) turns out to be more active than the zeolite, the chemoselectivity is elusive: compounds 2a,b undergo simultaneous S-methylation and esterification reactions, and acids 3-5 yield complex mixtures of products of O-methylation, O-methoxycarbonylation, and esterification of their OH and CO2H groups, respectively. Overall, the combined use of a nontoxic reagent/solvent (DMC) and a safe promoter (NaY) imparts a genuine ecofriendly nature to the investigated synthesis.
- Selva, Maurizio,Tundo, Pietro
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p. 1464 - 1470
(2007/10/03)
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- Bis (salicylaldehyde-1,2-phenylene diimine)Mn(III) chloride (Mn(III)-salophen) catalysed oxidation of thiols to symmetrical disulfides using urea hydrogen peroxide (UHP) as mild and efficient oxidant
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A variety of thiols were oxidised efficiently by a catalytic amount of Mn(III)-salophen 1 in the presence of urea hydrogen peroxide adduct 2 as a convenient and mild oxidant to afford the corresponding disulfides in high yields in quite short reaction tim
- Karami, Bahador,Montazerozohori, Morteza,Habibi, Mohammad Hossein
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p. 490 - 492
(2007/10/03)
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- Toward fully synthetic glycoproteins by ultimately convergent routes: A solution to a long-standing problem
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A method is disclosed for the convergent synthesis of multiply glycosylated peptides. The approach centers on a convergent technique for generating masked, complex glycopeptide-containing C-terminal acyl donors. Activation of the latent donor in situ and
- Warren, J. David,Miller, Justin S.,Keding, Stacy J.,Danishefsky, Samuel J.
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p. 6576 - 6578
(2007/10/03)
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- Chemistry of Sulfenic Acids. 7. Reason for the High Reactivity of Sulfenic Acids. Stabilization by Intramolecular Hydrogen Bonding and Electronegativity Effects
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It is proposed that the reason sulfenic acids (RSOH) are so reactive and usually not isolated or even detected is that they form thiosulfinates (RS(O)SR) so readily.This is a consequence of the sulfenic acid hydrogen-bonded dimer, 1, which lowers the energy of activation for thiosulfinate formation.The stability of the few sulfenic acids that have been isolated can be explained in terms of steric, electronic, and intramolecular hydrogen-bonding effects which prevent dimer formation.The importance of these effects on the stability of simple unstable sulfenic acids was demonstrated by flash vacuum pyrolysis (FVP) and the thiosulfinate/vinyl sulfoxide ratio.A novel, high yield, rearrangement of sulfenic acid 19f to 1,3-benzothiazine 26 was observed.
- Davis, Franklin A.,Jenkins, Linda A.,Billmers, Robert L.
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p. 1033 - 1040
(2007/10/02)
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- Oxidations with Lead Tetraacetate. V. Oxidations of 1,3-Benzoxathioles
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2,2-Disubstituted 1,3-benzoxathioles are easily oxidized by lead tetraacetate to a complex mixture of products.Acetoxylation takes place on the first carbon atom of the 2-alkyl or -cycloalkyl substituent giving acetoxy derivatives.The hetero ring is also opened yielding ketones, acetoxyketones, a disulfide and polymeric materials.Oxidation at the sulfur atom appears to be a minor reaction and no products oxidized in the benzene ring are found.
- Aromdee, Chantana,Cole, Edward R.,Crank, George
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p. 1255 - 1261
(2007/10/02)
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- CONFORMATIONAL CONSEQUENCES OF INTRAMOLECULAR HYDROGEN BONDING BY OH TO THE DIRECTIONAL LONE-PAIR OF SULFUR IN DERIVATIVES OF METHYL PHENYL SULFIDE, DIPHENYL SULFIDE, AND DIPHENYL DISULFIDE
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Complete spectral parameters for the 1H nmr spectra of 2-hydroxyphenyl methyl sulfide, 2, 2-hydroxyphenyl phenyl sulfide, 3, bis(2-hydroxy-3-tert-butyl-5-methylphenyl) sulfide, 4, and bis(2-hydroxyphenyl)disulfide, 5, are reported for CCl4 solu
- Schaefer, Ted,Salman, Salman R.,Wildman, Timothy A.,Clark, Peter D.
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p. 342 - 348
(2007/10/02)
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- Rearrangements and decompositions of thiobisphenols
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2,2′-, 2,4′- and 4,4′-Monothiobisphenol separately rearrange in phenol at 180° in the presence of sodium hydroxide to give similar mixtures containing only 2,2′-, 2,4′- and 4,4′-monothiobisphenol in the approximate ratio, 45:45:10. The rearrangements appear to be intermolecular and they are interpreted in terms of polar processes which lead initially to the formation of o- and p-monothiobenzoquinones. 2,2′-Dithiobisphenol, 4,4′-dithiobisphenol and 4,4′-trithiobisphenol under similar conditions are desulphurated with the evolution of hydrogen sulphide also to give mixtures containing only 2,2 - 2,4′- and 4,4′-monothiobisphenol whilst 3,3′-dithiobisphenol is stable in alkaline phenol even after long periods at 180°. Similar initial heterolyses to o- and p-monothiobenzoquinones are suggested as sources of the monothiobisphenols and displacements of sulphide- or hydrosulphide-ions from intermediate benzeneperthiolate ions by carbanions derived from phenol are suggested as sources of the hydrogen sulphide.
- Neale,Bain,Rawlings
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p. 4583 - 4591
(2007/10/05)
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