- 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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- Visible Light Induced Reduction and Pinacol Coupling of Aldehydes and Ketones Catalyzed by Core/Shell Quantum Dots
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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
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p. 2474 - 2488
(2021/02/05)
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- Metal-free chalcogenation of cycloketone oxime esters with dichalcogenides
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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
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supporting information
(2021/06/15)
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- Copper-catalyzedortho-selective direct sulfenylation ofN-aryl-7-azaindoles with disulfides
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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
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supporting information
p. 2901 - 2906
(2021/04/14)
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- Forging C?S(Se) Bonds by Nickel-catalyzed Decarbonylation of Carboxylic Acid and Cleavage of Aryl Dichalcogenides
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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
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p. 2452 - 2461
(2021/06/28)
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- B(C6F5)3-Catalyzed Electron Donor-Acceptor Complex-Mediated Aerobic Sulfenylation of Indoles under Visible-Light Conditions
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An efficient B(C6F5)3-catalyzed aerobic oxidative C-S cross-coupling reaction of thiophenol with indoles was developed, affording a wide range of diaryl sulfides in good yields. An electron donor-acceptor complex between B(C6F5)3 and indoles was formed, facilitating the photoinduced single-electron transfer (SET) from indole substrates to the B(C6F5)3 catalyst. This protocol demonstrates a new reaction model using B(C6F5)3 as a single-electron oxidant.
- Yuan, Wenkai,Huang, Jie,Xu, Xin,Wang, Long,Tang, Xiang-Ying
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supporting information
p. 7139 - 7143
(2021/09/14)
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- Extended Pummerer fragmentation mediated by carbon dioxide and cyanide
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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
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supporting information
(2020/10/30)
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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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- 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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- 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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- 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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- Preparation method for symmetric diaryl disulfide
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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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- 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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- Lewis Acid Promoted Aerobic Oxidative Coupling of Thiols with Phosphonates by Simple Nickel(II) Catalyst: Substrate Scope and Mechanistic Studies
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Exploring new catalysts for efficient organic synthesis is among the most attractive topics in chemistry. Here, using Ni(OAc)2/LA as catalyst (LA: Lewis acid), a novel catalyst strategy was developed for oxidative coupling of thiols and phosphonates to phosphorothioates with oxygen oxidant. The present study discloses that when Ni(OAc)2 alone was employed as the catalyst, the reaction proceeded very sluggishly with low yield, whereas adding non-redox-active metal ions such as Y3+ to Ni(OAc)2 dramatically promoted its catalytic efficiency. The promotional effect is highly Lewis acidity dependent on the added Lewis acid, and generally, a stronger Lewis acid provided a better promotional effect. The stopped-flow kinetics confirmed that adding Y(OTf)3 can obviously accelerate the activation of thiols by Ni(II) and next accelerate its reaction with phosphonate to generate the phosphorothioate product. ESI-MS characterizations of the catalyst disclosed the formation of the heterobimetallic Ni(II)/Y(III) species in the catalyst solution. Additionally, this Ni(II)/LA catalyst can be applied in the synthesis of a series of phosphorothioate compounds including several commercial bioactive compounds. This catalyst strategy has clearly supported that Lewis acid can significantly improve the catalytic efficiency of these traditional metal ions in organic synthesis, thus opening up new opportunities in their catalyst design.
- Xue, Jing-Wen,Zeng, Miao,Zhang, Sicheng,Chen, Zhuqi,Yin, Guochuan
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p. 4179 - 4190
(2019/04/30)
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- Making the SF5 Group More Accessible: A Gas-Reagent-Free Approach to Aryl Tetrafluoro-λ6-sulfanyl Chlorides
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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
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supporting information
p. 1950 - 1954
(2019/01/25)
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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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- Base-controlled Fe(Pc)-catalyzed aerobic oxidation of thiols for the synthesis of S-S and S-P(O) bonds
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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
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p. 4236 - 4242
(2018/06/21)
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- A One-Pot Cascade Reaction by Combining NH-Sulfoximines with Thiophenols Under Mild Conditions
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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
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p. 844 - 850
(2018/02/21)
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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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- 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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- Allylation and Alkylation of Biologically Relevant Nucleophiles by Diallyl Sulfides
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Allyl sulfides are bioactive phytochemicals found in garlic, onion, and other members of the genus Allium. Here we showed that diallyl disulfide and diallyl trisulfide can transfer allyl side chains to low molecular weight thiols. Diallyl monosulfide is i
- Viswanatharaju Ruddraraju, Kasi,Parsons, Zachary D.,Lewis, Calvin D.,Gates, Kent S.
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p. 776 - 780
(2017/04/26)
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- A practical synthesis of benzothiophenes via visible-light-promoted cyclization of disulfides and alkynes
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Visible-light-promoted intermolecular radical cyclization of disulfides and alkynes has been developed. Benzothiophenes bearing ester, ketone, aldehyde and aryl substituents were synthesized in good yields. The reaction was carried out in the absence of t
- Ye, Lin-Miao,Qian, Lu,Chen, Yan-Yan,Zhang, Xue-Jing,Yan, Ming
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supporting information
p. 550 - 554
(2017/01/25)
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- Solvent- and metal-free selective oxidation of thiols to disulfides using I2/DMSO catalytic system
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We describe herein a simple, fast and inexpensive protocol for the oxidative coupling of thiols employing a stoichiometric amount of DMSO and iodine as the catalyst. Various aromatic disulfides were obtained in good to excellent yields in short reaction times at room temperature, while aliphatic disulfides were achieved in good yields when the reactions were conducted under microwave irradiation.
- Bettanin, Luana,Saba, Sumbal,Galetto, Fábio Z.,Mike, Gustavo A.,Rafique, Jamal,Braga, Antonio L.
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supporting information
p. 4713 - 4716
(2017/11/21)
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- 18F-Fluoroform: A 18F-trifluoromethylating agent for the synthesis of SCF218F-aromatic derivatives
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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
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supporting information
p. 5706 - 5709
(2017/07/10)
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- IF5 affects the final stage of the Cl-F exchange fluorination in the synthesis of pentafluoro-λ6-sulfanyl-pyridines, pyrimidines and benzenes with electron-withdrawing substituents
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A difficult chlorine-fluorine (Cl-F) exchange fluorination reaction in the final stage of the preparation of pentafluoro-λ6-sulfanyl-(hetero)arenes having electron-withdrawing substituents has now been elucidated through the use of iodine pentafluoride. A major side-reaction of C-S bond cleavage was sufficiently inhibited by the potential interaction between F and I with a halogen bonding.
- Cui, Benqiang,Kosobokov, Mikhail,Matsuzaki, Kohei,Tokunaga, Etsuko,Shibata, Norio
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supporting information
p. 5997 - 6000
(2017/07/10)
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- Regiocontrolled direct C4 and C2-methyl thiolation of indoles under rhodium-catalyzed mild conditions
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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
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supporting information
p. 12197 - 12200
(2017/11/16)
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- Tunable and Practical Synthesis of Thiosulfonates and Disulfides from Sulfonyl Chlorides in the Presence of Tetrabutylammonium Iodide
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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
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supporting information
p. 3477 - 3481
(2016/11/13)
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- Synthesis of β-Hydroxysulfides from Thiophenols and Disulfides with tert-Butyl Hydroperoxide as the Oxidant and Reactant
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In this Communication, we developed a new procedure for the synthesis of β-hydroxysulfides from thiophenols or diaryl disulfides with TBHP as the oxidant. In the presence of zinc iodide or potassium iodide, with TBHP as the oxidant and pre-reactant, thiophenols and diaryl disulfides reacted with the methyl group of tBuOH smoothly and selectivity to give the corresponding 2-methyl-1-(arylthio)propan-2-ols as the terminal products in moderate to good yields.
- Feng, Jian-Bo,Wu, Xiao-Feng
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p. 315 - 318
(2016/08/19)
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- General and practical formation of thiocyanates from thiols
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A new method for the cyanation of thiols and disulfides using cyanobenziodoxol(on)e hypervalent iodine reagents is described. Both aliphatic and aromatic thiocyanates can be accessed in good yields in a few minutes at room temperature starting from a broad range of thiols with high chemioselectivity. The complete conversion of disulfides to thiocyanates was also possible. Preliminary computational studies indicated a low energy concerted transition state for the cyanation of the thiolate anion or radical. The developed thiocyanate synthesis has broad potential for various applications in synthetic chemistry, chemical biology and materials science.
- Frei, Reto,Courant, Thibaut,Wodrich, Matthew D.,Waser, Jerome
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p. 2662 - 2668
(2015/02/05)
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- Metal-Free Photocatalytic Aerobic Oxidation of Thiols to Disulfides in Batch and Continuous-Flow
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Disulfides represent significant molecular and structural features in various biologically active compounds and fine chemicals. Therefore, the development of mild, efficient and sustainable methods to access disulfides is of great importance. Here, we describe the development of a mild metal-free photocatalytic aerobic oxidation of thiols to disulfides using Eosin Y and visible-light irradiation. A continuous flow procedure was developed to accelerate the photocatalytic process, enabling the preparation of disulfides with high purity in a timeframe of minutes. The mildness and applicability of our method was exemplified by the flow synthesis of the cyclic peptide hormone, oxytocin, requiring only a 200s reaction time and an efficient one-pot batch protocol for the preparation of the therapeutic thiuram disulfide, disulfiram.
- Talla, Ali,Driessen, Brian,Straathof, Natan J. W.,Milroy, Lech-Gustav,Brunsveld, Luc,Hessel, Volker,No?l, Timothy
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supporting information
p. 2180 - 2186
(2015/07/27)
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- Mild and selective catalytic oxidation of organic substrates by a carbon nanotube-rhodium nanohybrid
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A heterogeneous catalyst was assembled by stabilization of rhodium nanoparticles on carbon nanotubes. The nanohybrid was used for the catalytic aerobic oxidation of diverse substrates such as hydroquinones, hydroxylamines, silanes, hydrazines and thiols, at room temperature. The system proved very efficient on the investigated substrates and demonstrated high selectivity.
- Donck, Simon,Gravel, Edmond,Li, Alex,Prakash, Praveen,Shah, Nimesh,Leroy, Jocelyne,Li, Haiyan,Namboothiri, Irishi N. N.,Doris, Eric
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p. 4542 - 4546
(2015/09/01)
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- Mechanistic insights into the interface-directed transformation of thiols into disulfides and molecular hydrogen by visible-light irradiation of quantum dots
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Quantum dots (QDs) offer new and versatile ways to harvest light energy. However, there are few examples involving the utilization of QDs in organic synthesis. Visible-light irradiation of CdSe QDs was found to result in virtually quantitative coupling of a variety of thiols to give disulfides and H2 without the need for sacrificial reagents or external oxidants. The addition of small amounts of nickel(II) salts dramatically improved the efficiency and conversion through facilitating the formation of hydrogen atoms, thereby leading to faster regeneration of the ground-state QDs. Mechanistic studies reveal that the coupling reaction occurs on the QD surfaces rather than in solution and offer a blueprint for how these QDs may be used in other photocatalytic applications. Because no sacrificial agent or oxidant is necessary and the catalyst is reusable, this method may be useful for the formation of disulfide bonds in proteins as well as in other systems sensitive to the presence of oxidants. Copyright
- Li, Xu-Bing,Li, Zhi-Jun,Gao, Yu-Ji,Meng, Qing-Yuan,Yu, Shan,Weiss, Richard G.,Tung, Chen-Ho,Wu, Li-Zhu
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supporting information
p. 2085 - 2089
(2014/03/21)
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- Flavin-catalyzed aerobic oxidation of sulfides and thiols with formic acid/triethylamine
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An efficient and practical catalytic method for the aerobic oxidative transformation of sulfides into sulfoxides, and thiols into disulfides with formic acid/TEA in the presence of a new, readily available, and stable flavin catalyst 5d is described. This journal is the Partner Organisations 2014.
- Murahashi, Shun-Ichi,Zhang, Dazhi,Iida, Hiroki,Miyawaki, Toshio,Uenaka, Masaaki,Murano, Kenji,Meguro, Kanji
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supporting information
p. 10295 - 10298
(2014/08/18)
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- Divergent synthesis and tuning of the electronic structures of cobalt-dithiolene-fullerene complexes for organic solar cells
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A pentakis(aryl)[60]fullerene cobalt trisulfide complex (1a) was obtained from the reaction of a pentakis(aryl)[60]fullerene cobalt dicarbonyl complex (2a) with triphenylmethanethiol. This reaction proceeded smoothly even at ambient temperature to produce 1a in moderate to high yield. The series of pentakis(aryl)[60]fullerene cobalt dithiolene complexes 3-9 were also synthesized by the reaction of 1a with a variety of readily available disulfide compounds. The HOMO and LUMO levels of the complexes could be tuned by making changes to the substituents on the dithiolene ligands, with changes to the electronic structure of the compounds influencing their photovoltaic performance, especially in terms of their open-circuit voltage. Small-molecule organic solar cells constructed from the naphthalene dithiolene complex 9 and tetrabenzoporphyrin showed a power conversion efficiency of 0.59%.
- Matsuo, Yutaka,Ogumi, Keisuke,Maruyama, Masashi,Nakagawa, Takafumi
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p. 659 - 664
(2014/03/21)
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- Copper-mediated oxidative trifluoromethylthiolation of aryl boronic acids with CF3CO2Na and elemental sulfur
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A practical three-component copper-mediated oxidative trifluoromethylthiolation of aryl boronic acids with cheap and readily available sodium trifluoroacetate and elemental sulfur is reported. A variety of trifluoromethylthio-substituted aromatics are synthesized in moderate yields under mild reaction conditions.
- Zhai, Lijuan,Li, Yaming,Yin, Jun,Jin, Kun,Zhang, Rong,Fu, Xinmei,Duan, Chunying
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p. 10262 - 10266
(2013/11/19)
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- METHOD FOR PRODUCING DISULFIDE
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The present invention relates to an industrial method for producing diphenyl disulfide that may have a substituent, and to an industrially advantageous method for producing a high-purity disulfide with high yield and low environmental load. An object of the present invention is to provide an industrially advantageous method for producing high-purity diphenyl disulfide that may have a substituent with high yield and low environmental load. The object is achieved by providing a production method including a step of heating thiophenol that may have a substituent under pressure in water in the presence of a basic inorganic salt and oxygen to cause oxidation and a step of separating diphenyl disulfide that is produced in the previous step and may have a substituent.
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Page/Page column 7
(2013/07/19)
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- Metal-templated ligand architectures for trinuclear chemistry: Tricopper complexes and their O2 reactivity
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A trinucleating framework was assembled by templation of a heptadentate ligand around yttrium and lanthanides. The generated complexes orient three sets of two or three N-donors each for binding additional metal centers. Addition of three equivalents of c
- Lionetti, Davide,Day, Michael W.,Agapie, Theodor
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p. 785 - 790
(2013/03/28)
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- Synthetic glutathione peroxidase mimics: Effect of nucleophilicity of the aryl thiol cofactor on the antioxidant activity
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Catalytic activity of a series of potent amide- and amine-based organoselenium compounds are studied in the presence of various aromatic thiols having electron donating and electron withdrawing substituents on the phenyl ring. This study suggests that the
- Bhabak, Krishna Pada,Bhowmick, Debasish,Mugesh, Govindasamy
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p. 1019 - 1025
(2013/09/12)
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- Synthesis of diaryl disulfides via mild reduction of arylsulfinates with hydrazine monohydrate in DMSO
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Arylsulfinates were reduced with hydrazine monohydrate at room temperature in dimethylsulfoxide (DMSO) to afford diaryl disulfides in good yields. A dramatic solvent effect was observed, and DMSO was found to be the best solvent for the reaction. Copyright Taylor & Francis Group, LLC.
- Zhu, Rui-Heng,Shi, Xiao-Xin
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experimental part
p. 1108 - 1114
(2012/04/04)
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- Synthesis and reactivity of dipropargylic disulfides: tandem rearrangements, cyclization, and oxidative dimerization
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Synthesis and facile rearrangement and cyclization reaction of new dipropargylic disulfides are described. A possible mechanism for these transformations involving an initial double [2,3]-sigmatropic rearrangement to the elusive diallenyl disulfides via a thiosulfoxide intermediates is suggested.
- Braverman, Samuel,Cherkinsky, Marina,Meridor, David,Sprecher, Milon
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experimental part
p. 1925 - 1930
(2010/04/24)
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- Oxidative transformation of thiols to disulfides promoted by activated carbon-air system
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Efficient oxidative transformation of thiols to disulfides took place in the presence of activated carbon under an oxygen (or air) atmosphere. The present oxidation method is available not only for a variety of thiols such as simple aromatic and aliphatic thiols but also for 3,4-dihydropyrimidin-2(1H)- thiones and N-Boc-l-cysteine.
- Hayashi, Masahiko,Okunaga, Ken-Ichi,Nishida, Shunsuke,Kawamura, Kenjiro,Eda, Kazuo
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supporting information; experimental part
p. 6734 - 6736
(2011/02/25)
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- Oxidation/reduction interconversion of thiols and disulfides using hydrogen and oxygen catalyzed by a rhodium complex
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RhH(PPh3)4 catalyzes reduction of disulfides to thiols by hydrogen and RhH(PPh3)4/1,4- bis(diphenylphosphino)butane (dppb) catalyzes oxidation of thiols to disulfides by oxygen.
- Arisawa, Mieko,Sugata, Chiyoshi,Yamaguchi, Masahiko
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p. 6097 - 6099
(2007/10/03)
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- Oxidative coupling of thiols to disulfides using a solid anhydrous potassium phosphate catalyst
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Thiols are oxidized to the corresponding disulfides with a mild base, anhydrous potassium phosphate, under ambient conditions in the presence of air.
- Joshi, Ashutosh V.,Bhusare, Sudhakar,Baidossi, Mubeen,Qafisheh, Nida,Sasson, Yoel
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p. 3583 - 3585
(2007/10/03)
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- Electronic properties of para-substituted thiophonols and disulfides from 13C NMR spectroscopy and ab initio calculations: Relations to the Hammett parameters and atomic charges
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A large number of para-substituted benzene thiols and the corresponding disulfides were synthesized and characterized by 1H NMR, 13C NMR, and IR spectroscopies. Geometrics of all sixteen thiols and fourteen disulfide compounds were optimized at the B3LYP/6-31G(d) level, while the electronic structure and the 13C isotropic shifts were calculated by ab initio Hartree-Fock method coupled with the Gauge-Independent Atomic Orbital (GIAO) algorithm and a 6-31+G(d,p) basis set. The calculated 13C NMR isotropic shifts exhibit admirable agreement (δ rmsd ~4.6 ppm) with the experimental data. The chemical shift of para-substituted carbon showed a linear correlation with Hammett constants (σp and σn+). Using this methodology the σp+ constants for the dendritic ligands have been estimated to be 0.25 and 0.24 for 2(n) and 2(o), respectively. In addition, the NBO charges on the sulfur atoms shows a latent response with the σp+ parameter. The atomic charge on the thiophenolato sulfur is invariant with the electron withdrawing ability of the substituents, however, the charge increases with increasing electron-withdrawing power.
- Sengar, Raghvendra S.,Nemykin, Victor N.,Basu, Partha
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p. 1115 - 1123
(2007/10/03)
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- Unexpected deoxygenation of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) by thiyl radicals through the formation of arylsulphinyl radicals
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2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), upon reaction with thiophenols, undergoes deoxygenation leading mainly to the formation of tetramethylpiperidinium arylsulphinates and arylsulphonates. Other identified products of the reaction are aryldisulphides, 2,2,6,6-tetramethylpiperidine, S-aryl-arylthiosulphonates, N-arylsulphinyl- and N-arylsulphonyl-2,2,6,6-tetramethylpiperidine. The formation of the reaction products is discussed on the basis of the interaction of arylsulphinyl and arylsulphonyl radicals with TEMPO as well as on the basis of the evolution of the arylsulphinyl radical itself.
- Carloni,Carloni, Patricia,Damiani,Damiani, Elisabetta,Iacussi,Iacussi, Marco,Greci,Greci, Lucedio,Stipa,Stipa, Pierluigi,Cauzi,Cauzi, Daniele,Rizzoli,Rizzoli, Corrado,Sgarabotto,Sgarabotto, Paolo
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p. 12445 - 12452
(2007/10/02)
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- Phthalimidomethyl Group. A New Protecting Group of Thiols
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Phthalimidomethyl group is employed as a protecting group of thiols.This group can be introduced to thiols under mild reaction conditions and be removed by treatment with hydrazine hydrate followed by mercuric acetate or cupric acetate.
- Gong, Young-Dae,Iwasawa, Nobuharu
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p. 2139 - 2142
(2007/10/02)
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- Direct aromatic tert-butylation during the synthesis of thiochroman-4-ones
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The synthesis of thiochroman-4-ones from thiophenols and 3-methylbut-2-enoic acid effected by methane sulphonic acid is accompanied by tert-butylation of the aromatic ring. 3-Arylthiobutanoic acids, available using β-butyrolactone, are efficiently cyclised in the same manner.
- Clayton, Stephen E.,Gabbutt, Christopher D.,Hepworth, John D.,Mark Heron
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p. 939 - 946
(2007/10/02)
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- Electrooxidation of thiols in the presence of halide ions - A facile preparative method for synthesis of disulfides
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The aliphatic, aromatic and heteroaromatic disulfides were easily synthesized by the electrolysis of corresponding thiols. The electrochemical method is also convenient for synthesis of unsymmetrically substituted disulfides and 'paired' synthesis of disu
- Niyazymbetov,Konyushkin,Niyazymbetova,Litvinov,Petrosyan
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p. 1659 - 1665
(2007/10/02)
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- Efficient, high yield oxidation of thiols and selenols to disulphides and diselenides
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Thiols and selenols are smoothly oxidised in high yield to disulphides and diselenides by sodium perborate at room temperature.
- McKillop,Koyuncu,Krief,Dumont,Renier,Trabelsi
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p. 5007 - 5010
(2007/10/02)
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- Substituent Effects on the Free-radical Addition Reactions of Arylthiyl Radicals with Arylacetylenes
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Absolute rate constants for addition reactions of arylthiyl radicals (YC6H4S.) to arylacetylenes (XC6H4CCH) have been determined by a flash-photolysis method.The rate constants (in dm3 mol-1 s-1) vary from 1.
- Ito, Osamu,Fleming, Maria Daniela C. M.
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p. 689 - 694
(2007/10/02)
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