- Utilizing 2-phenylpropanal as coupling partner for C-S bond formation via sequential thioarylation and decarbonylation process: A novel strategy for the synthesis of aryl alkyl sulfides
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In this study, first direct access to aryl alkyl sulfides employing 2-phenylpropanal as coupling partner is reported. Diaryl disulfides react with this aldehyde in the presence of morpholine and produce the corresponding sulfide products in high yields. In another part, disulfides are in situ generated in the reaction mixture from aryl halides/CuI/Cyanodithioformate and coupled with 2-phenylpropanal to access aryl alkyl sulfides.
- Shaikhi Shahidzadeh, Elham,Nowrouzi, Najmeh,Abbasi, Mohammad
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- Ligand-free copper-catalysed direct synthesis of diaryl sulfides and diaryl disulfides in wet poly(ethylene glycol)
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An improved protocol has been developed for the one-pot CuI-catalysed preparation of symmetric diaryl sulfides from their available aryl halides in the presence of thiourea as sulfur transfer agent and in the absence of both ligand and organic solvent. This catalytic system was also used for the high-yielding preparation of diaryl disulfides in the presence of C2Cl6 as oxidant.
- Nowrouzi, Najmeh,Abbasi, Mohammad,Latifi, Hadis
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- Europhtal (8020) efficiently catalyzes the aerobic oxidation of in situ generated thiols to symmetric disulfides (disulfanes)
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Efficient, odorless and scalable synthetic protocols have been introduced for the preparation of symmetric alkyl disulfides by treatment of the corresponding organic halides with thiourea and NaHCO3in the presence of commercially available Europhtal catalyst (8020) in both H2O and poly ethylene glycol (PEG-200) media at 80–90 °C. Structurally diverse primary, secondary, allylic and benzylic halides were examined successfully whereas, the result with tert-butyl bromide was not satisfactory. Also, another procedure has been introduced for achieving symmetric aryl disulfides in high yields by reacting aryl halides, thiourea and NaHCO3in PEG-200 at 115–120 °C using CuI along with Europhtal catalysts. The results showed that the aerobic oxidation of in situ generated thiols proceeded efficiently in the presence of Europhtal catalyst giving the symmetric disulfide without contamination by symmetric sulfide side-product.
- Abbasi, Mohammad,Sabet, Askar,Sabet, Askar
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- 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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- Visible-light-mediated facile synthesis of disulfides using reusable TiO2/MoS2nanocomposite photocatalyst
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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
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supporting information
p. 1268 - 1274
(2016/08/16)
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- Catalyst-Free, Regioselective Ring Opening of Donor-Acceptor Cyclopropanes: Synthesis of Functionalized Mono- and Disulfides
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Interesting sulfur compounds such as monosulfides, symmetrical disulfides, unsymmetrical disulfides, and other 1,3-bifunctionalized compounds were synthesized using benzyltriethylammonium tetrathiomolybdate, [BnNEt3]2MoS4, as the sulfur transfer reagent via regioselective ring opening of donor-acceptor cyclopropanes without the addition of any catalyst.
- Gopinath, Purushothaman,Chandrasekaran, Srinivasan
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p. 3087 - 3096
(2016/09/09)
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- Selective synthesis of organic sulfides or disulfides by solvent exchange from aryl halides and KSCN catalyzed by NiCl2·6H2O
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A method for selective synthesis of symmetric sulfides or disulfides from the reaction of aryl halides with KSCN by solvent exchange is introduced. Aryl halides were selectively converted to the symmetric disulfides or sulfides in high yields when they are treated with KSCN in the presence of NiCl2·6H2O and DMAP at 140?°C in DMF or poly ethylene glycol (PEG-200) respectively.
- Abbasi, Mohammad,Nowrouzi, Najmeh,Latifi, Hadis
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p. 112 - 117
(2016/09/07)
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- 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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- Haloacid/dimethyl sulfoxide-catalyzed synthesis of symmetrical disulfides by oxidation of thiols
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A novel method is developed for the oxidation of thiols to the corresponding disulfides using 20 mol % haloacid (HBr or HI) in combination with dimethyl sulfoxide. A tentative mechanism is proposed for the oxidation. In addition to the advantages of cost-effectiveness, simple processes, and broad functional group tolerance, the exclusive formation of disulfides is the principle reward of this methodology while compared to known methods that further oxidize disulfides to S-oxides and other byproducts.
- Natarajan, Palani,Sharma, Himani,Kaur, Mandeep,Sharma, Pooja
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supporting information
p. 5578 - 5582
(2015/09/21)
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- Deep eutectic mixture catalysed the synthesis of disulfides using Bunte salts as thiol surrogates
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Bunte salts, easily prepared from odourless sodium thiosulfates and various alkyl and aryl halides, acted as thiol surrogates for preparation of disulfides in the presence of hydrogen peroxide and a Bronsted-acidic deep eutectic mixture. The reaction proceeded smoothly to give the corresponding disulfide products in moderate to good yields, leaving odourless sodium bisulfite and water as the by-products. Moreover, this catalytic system could be readily recovered and reused several times without significant loss in activity.
- Zhou, Yongsheng
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p. 332 - 335
(2015/08/18)
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- The Chan-Lam reaction of chalcogen elements leading to aryl chalcogenides
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A copper-catalyzed chalcogenation of arylboronic acids with elemental sulfur or selenium is established, which provides diaryl disulfides or diaryl monoselenides in moderate to good yields with excellent selectivities, respectively. Moreover, after sequential reduction and coupling with aryl/alkyl iodides in one pot, unsymmetrical monosulfides were obtained in good yields.
- Yu, Jin-Tao,Guo, Huan,Yi, Yuanqiuqiang,Fei, Haiyang,Jiang, Yan
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supporting information
p. 749 - 752
(2014/04/03)
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- Use of base control to provide high selectivity between diaryl thioether and diaryl disulfide for C-S coupling reactions of aryl halides and sulfur and a mechanistic study
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Previous studies have reported that S-arylation produces diaryl disulfide when the precursors include sulfur powder and aryl halide using CuI as the catalyst. However, our research has revealed that the use of different bases in the above S-arylation process results in the coproduction of diarylsulfane and diaryldisulfane. In addition, we have demonstrated that the ratio of the two products can be controlled by selecting the alkalinity of the bases. 1H NMR spectra showed that diaryldisulfane was the first product, which became the reagent in a reaction with aryl halide to form diarylsulfane through CuI catalysis. Various aryl halides were tested to enhance the selectivity between diarylsulfane and diaryldisulfane using various different bases, leading to the following principles. A weak base, such as metal carbonate or acetate, results in the production of only diaryldisulfane; a strong base, such as metal hydroxide, results in the production of both diaryldisulfane and diarylsulfane. According to DFT calculations, hydroxide ions, which were exchanged for iodide and bonded with Cu, affected Cu electrons more strongly to reduce diaryl disulfide.
- Chen, Hsing-Ying,Peng, Wei-Te,Lee, Ying-Hsien,Chang, Yu-Lun,Chen, Yen-Jen,Lai, Yi-Chun,Jheng, Nai-Yuan,Chen, Hsuan-Ying
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p. 5514 - 5522
(2013/11/06)
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- Synthesis of diaryl disulfides via the reductive coupling of arylsulfonyl chlorides
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A facile synthesis of diaryl disulfides from arylsulfonyl chlorides in the presence of triphenylphosphine has been developed.
- Kabalka, George W.,Reddy, Marepally Srinivasa,Yao, Min-Liang
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scheme or table
p. 7340 - 7342
(2010/03/01)
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- A direct preparation of functionalized aryl and heteroaryl disulfides from functionalized zinc organometallics by using sulfur monochloride (S 2Cl2)
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A range of functionalized aryl and heteroaryl disulfides has been prepared from zinc organometallics by using sulfur monochloride (S2Cl 2). The zinc reagents were obtained by transmetalation from magnesium or lithium reagents with ZnBr2.
- Korn, Tobias J.,Knochel, Paul
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p. 1185 - 1187
(2007/10/03)
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- Aryl monosulphides and symmetrical disulphides based second order nonlinear optical chromophores with transparency in the visible
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A series of aryl monosulphides and disulphides have been synthesized and characterized. Their molecular hyperpolarizability (β) has been measured in solution with the hyper-Rayleigh Scattering technique and also calculated by semiempirical AM1 method. The trend in the observed and calculated values of first hyperpolarizability of these compounds has been found to be in good agreement. These compounds show moderate β values and excellent transparency in the visible region.
- Sudharsanam, Ramanathan,Chandrasekaran, Srinivasan,Das, Puspendu Kumar
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p. 1763 - 1766
(2007/10/03)
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- A biomimetic methyl transfer from amine to thiol
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A biomimetic methyl transfer, analogous to a tetrahydrofolate-to-homocystein transfer, is simulated by the reaction of methylammonium salts with arylthiolatocobaloxime; the mechanism proposed is an electron transfer from the cobaloxime to the ammonium ion followed by radical substitution of the methyl group.
- Tada, Masaru,Kambe, Tohru,Inouye, Yoshinobu
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- Nucleophilic properties of thiourea towards aromatic halides
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Arylsulfides (and diaryldisulfides obtained spontaneously by oxidation of the arylsulfides during the work-up) and diarylsulfides can be obtained by substituting aryl radicals by the thiourea onion in liquid ammonia under an electrochemical inducement.
- Combellas,Dellerue,Mathey,Thiebault
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p. 539 - 542
(2007/10/03)
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- Nonchain processes in nucleophilic substitutions triggered by electron transfer (SRN1). Photochemical and electrochemical induction of the substitution of 1-iodoadamantane by arenethiolate ions
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Photochemical induction of the reaction of 1-iodoadamantane with arenethiolate ions provides a clear-cut example of nonchain SRN1 substitutions. With 4-methoxy-, 4-methyl-, and 4-cyanobenzene and benzenethiolate ions, excellent yields (over 85%) are obtained in spite of efficient electron transfer quenching of the very easily oxidized anion radical of the substituted product by quaternary ammonium countercations. The production of the corresponding disulfides is used to determine the number of chains. Absorption and fluorescence spectroscopy and laser pulse irradiation experiments indicate that the electron which triggers the substitution process is generated by photoejection from the nucleophile, with an efficiency that decreases in the order 4-methoxybenzene > 4-methyl-benzene > 4-benzene > 4-cyanobenzenethiolate. Electron photoejection does not occur with naphthalenethiolate ions. However substitution can be entrained by addition of benzenethiolate ions. The two nucleophiles were found to have comparable reactivities toward the 1-adamantyl radical. Rather than the formation of its anion radical, the first step of the SRN1 process is a dissociative electron transfer to 1-iodoadamantane, yielding directly the adamantyl radical. This is the reason that direct electrochemical induction of the substitution was not observed. Induction by electrogenerated aromatic anion radicals could be observed. It was much less efficient than photoinduction because the amount of electron donor species required to trigger the reaction is much larger.
- Ahbala, Mustapha,Hapiot, Philippe,Houmam, Abdelaziz,Jouini, Mohamed,Pinson, Jean,Savéant, Jean-Michel
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p. 11488 - 11498
(2007/10/03)
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- Two efficient and practical syntheses of methyl 4-mercaptobenzoate
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Two efficient syntheses of methyl-4-mercaptobenzoate are described, one utilizing the dianion of 4-bromothiophenol, the other a S(N)Ar reaction starting with 4-fluorobenzonitrile.
- Tickner,Huang,Gombatz,Mills,Novack,Webb
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p. 2497 - 2505
(2007/10/02)
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- Rapid and Selective Reduction of Functionalized Aromatic Disulfides with Lithium Tri-tert-butoxyaluminohydride. A Remarkable Steric and Electronic Control. Comparison of Various Hydride Reagents
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Lithium tri-tert-butoxyaluminohydride (LTBA), an exceptionally mild reducing agent in organic synthesis, reduces functionalized aromatic disulfides to the corresponding thiols in quantitative yield.The reaction is rapid (for example, o-tolyl disulfide is reduced to completion in 60 min at 25 deg C) and can tolerate a wide variety of functional groups, such as halogen, nitro, carboxylic acid, and their derivatives.The presence of electron-withdrawing substituents dramatically enhances the rate of reduction (p-chlorophenyl disulfide is quantitatively reduced in 30 s) and electron-releasing substituents diminishes the rate of cleavage.The reaction is sensitive to steric effects (2,4-di-tert-pentylphenyl disulfide underwent 25percent reduction in 24 h).However, such hindered disulfides can be rapidly and quantitatively reduced in refluxing THF.The reaction of LTBA with alkyl disulfides is extremely sluggish.The reaction provides a useful and simple means for the facile and selective reduction of aromatic disulfides where this is required in synthetic operations.
- Krishnamurthy, S.,Aimino, D.
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p. 4458 - 4462
(2007/10/02)
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