- Synthesis of benzyl thioether derivatives via N-heterocyclic carbene palladium(II)-catalyzed cross coupling of benzylammonium salts with thiophenols
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A new route to benzyl thioether derivatives has been developed via the N-heterocyclic carbene palladium(II)-catalyzed cross coupling of benzylammonium salts with thiophenols. Under the optimal conditions, different benzylammonium salts could be well toler
- Wang, Tao,Guo, Jiarui,Xu, Yongli,Wang, Xiaobo,Wang, Yan,Feng, Dandan,Liu, Lantao
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- Transition-Metal-Free and Base-Promoted Carbon-Heteroatom Bond Formation via C-N Cleavage of Benzyl Ammonium Salts
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A facile and general method for constructing carbon-heteroatom (C-P, C-O, C-S, and C-N) bonds via C-N cleavage of benzyl ammonium salts under transition-metal-free conditions was reported. The combination of t-BuOK and 18-crown-6 enabled a wide range of substituted benzyl ammonium salts to couple readily with different kinds of heteroatom nucleophiles, i.e. hydrogen phosphoryl compounds, alcohols, thiols, and amines. Good functional group tolerance was demonstrated. The scale-up reaction and one-pot synthesis were also successfully performed.
- Liu, Long,Tang, Yuanyuan,Wang, Kunyu,Huang, Tianzeng,Chen, Tieqiao
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p. 4159 - 4170
(2021/03/09)
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- Mono- And Dinuclear α-Diimine Nickel(II) and Palladium(II) Complexes in C-S Cross-Coupling
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The usefulness of transition metal catalytic systems in C-S cross-coupling reactions is significantly reduced by air and moisture sensitivity, as well as harsh reaction conditions. Herein, we report four highly air- and moisture-stable well-defined mononuclear and bridged dinuclear α-diimine Ni(II) and Pd(II) complexes for C-S cross-coupling. Various ligand frameworks, including acenaphthene- and iminopyridine-based ligands, were employed, and the resulting steric properties of the catalysts were evaluated and correlated with reaction outcomes. Under aerobic conditions and low temperatures, both Ni and Pd systems exhibited broader substrate scope and functional group tolerance than previously reported catalysts. Over 40 compounds were synthesized from thiols containing alkyl, benzyl, and heteroaryl groups. Also, pharmaceutically active heteroaryl moieties are incorporated from thiol and halide sources. Notably, the bridged dinuclear five-coordinate Ni complex has outperformed the remaining three mono four- or six-coordinate complexes by giving almost quantitative yields across a broad substrate scope.
- Talukder, Md Muktadir,Miller, Justin T.,Cue, John Michael O.,Udamulle, Chinthaka M.,Bhadran, Abhi,Biewer, Michael C.,Stefan, Mihaela C.
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- Synthesis of benzyl sulfidesviasubstitution reaction at the sulfur of phosphinic acid thioesters
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An ambident electrophilicity of phosphinic acid thioesters is disclosed. Unexpected carbon-sulfur bond formation took place in the reaction between phosphinic acid thioesters and benzyl Grignard reagents. The developed method for benzyl sulfides has a wide substrate scope and was applicable for the synthesis of a drug analog.
- Nishiyama, Yoshitake,Hosoya, Takamitsu,Yoshida, Suguru
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supporting information
p. 5771 - 5774
(2020/06/03)
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- Synthesis and characterization of Pd(II) complexes bearing NS, CS, SNS and SCS ligands. Evaluation of their microwave assisted catalytic activity in C–C coupling reactions
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A series of coordination (Pd-NS, Pd-SNS, Pd-SNS-O) and organometallic (Pd-C and Pd-SCS) Pd(II) complexes supported by bidentate and tridentate ligands featuring sulphur moieties have been prepared. All ligands and their palladium complexes were fully char
- Aguilar-Castillo, Bethsy A.,Gabriel Flores-Rojas, G.,González-Sebastián, Lucero,Hernández-Ortega, Simón,Morales-Morales, David,Reyes-Martínez, Reyna
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- Nanolayered cobalt-molybdenum sulphides (Co-Mo-S) catalyse borrowing hydrogen C-S bond formation reactions of thiols or H2S with alcohols
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Nanolayered cobalt-molybdenum sulphide (Co-Mo-S) materials have been established as excellent catalysts for C-S bond construction. These catalysts allow for the preparation of a broad range of thioethers in good to excellent yields from structurally diverse thiols and readily available primary as well as secondary alcohols. Chemoselectivity in the presence of sensitive groups such as double bonds, nitriles, carboxylic esters and halogens has been demonstrated. It is also shown that the reaction takes place through a hydrogen-autotransfer (borrowing hydrogen) mechanism that involves Co-Mo-S-mediated dehydrogenation and hydrogenation reactions. A novel catalytic protocol based on the thioetherification of alcohols with hydrogen sulphide (H2S) to furnish symmetrical thioethers has also been developed using these earth-abundant metal-based sulphide catalysts.
- Corma, Avelino,Sorribes, Iván
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p. 3130 - 3142
(2019/03/13)
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- Synthesis and radioprotective effects of novel benzyl naphthyl sulfoxide (sulfone) derivatives transformed from Ex-RAD
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In this work, a series of novel benzyl naphthyl sulfoxides (sulfones) derived from Ex-RAD were designed and synthesized as potential radioprotective agents. Some of the compounds considerably protected HUVECs against 60Co γ-irradiation, accompanied by the absence of cytotoxicity. Compared to Ex-RAD, compound 8n not only exhibited a significant protective effect on cell survival and radiation-induced DNA damage, but also remarkably enhanced the survival (100%) of mice in 30 days after being exposed to irradiation. The results suggested that some target compounds are valuable for further research as promising radioprotectors.
- Tang, Lin,Peng, Tao,Wang, Gang,Wen, Xiaoxue,Sun, Yunbo,Zhang, Shouguo,Liu, Shuchen,Wang, Lin
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supporting information
p. 625 - 631
(2018/05/03)
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- A Novel Method for the Direct Synthesis of Symmetrical and Unsymmetrical Sulfides and Disulfides from Aryl Halides and Ethyl Potassium Xanthogenate
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An efficient and new method for the synthesis of disulfides and sulfides via the reaction of aryl halides with ethyl potassium xanthogenate in the presence of MOF-199 is described. O -Ethyl- S -aryl carbonodithioate has a key role as an intermediate in this procedure; it was converted into symmetrical diaryl disulfides in DMF. Additionally, this could be applied to the synthesis of unsymmetrical aryl alkyl(aryl′) disulfides by the reaction with S -alkyl(aryl) sulfurothioates (Bunte salts) as well as unsymmetrical aryl alkyl(aryl′) sulfides in DMSO.
- Soleiman-Beigi,Arzehgar
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supporting information
p. 986 - 992
(2018/02/09)
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- Efficient dehydrative alkylation of thiols with alcohols catalyzed by alkyl halides
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Alcohols can be efficiently converted into the useful thioethers by a transition metal- and base-free dehydrative S-alkylation reaction with thiols or disulfides by employing alkyl halides as the effective catalyst. This simple and efficient method is a green and practical way for the preparation of thioethers, as it tolerates a wide range of substrates such as aryl and alkyl thiols, as well as benzylic, allylic, secondary, tertiary, and even the less reactive aliphatic alcohols.
- Yang, Yaqi,Ye, Zihang,Zhang, Xu,Zhou, Yipeng,Ma, Xiantao,Cao, Hongen,Li, Huan,Yu, Lei,Xu, Qing
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supporting information
p. 9638 - 9642
(2017/11/30)
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- Rhodium-Catalyzed ipso-Borylation of Alkylthioarenes via C-S Bond Cleavage
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Rhodium-catalyzed transformation of alkyl aryl sulfides into arylboronic acid pinacol esters via C-S bond cleavage is reported. In combination with transition-metal-catalyzed sulfanyl group-guided regioselective C-H borylation reactions of alkylthioarenes, this method allows the synthesis of a diverse range of multisubstituted arenes.
- Uetake, Yuta,Niwa, Takashi,Hosoya, Takamitsu
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supporting information
p. 2758 - 2761
(2016/06/15)
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- Mesolysis Mechanisms of Aromatic Thioether Radical Anions Studied by Pulse Radiolysis and DFT Calculations
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The mesolysis mechanisms for eight aromatic thioether radical anions (ArCH2SAr′?-) generated during radiolysis in 2-methyltetrahydrofuran were studied by spectroscopic measurements and DFT calculation. Seven of ArCH2SAr′s
- Yamaji, Minoru,Tojo, Sachiko,Fujitsuka, Mamoru,Sugimoto, Akira,Majima, Tetsuro
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p. 7890 - 7895
(2015/09/01)
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- One-pot palladium-catalyzed borrowing hydrogen synthesis of thioethers
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Palladium on magnesium oxide is able to allow a one-pot reaction to synthesize thioethers from thiols and aldehydes formed in situ from the respective alcohol by means of a borrowing hydrogen method. The reaction is initiated by dehydrogenation of the alcohol to give a palladium hydride intermediate and an aldehyde. The latter reacts with a thiol involving most probably the intermediacy of a thionium ion RCHi£S+R, which can be reduced in situ by the metal hydride to afford thioethers. Lending support: Palladium nanoparticles on MgO catalyze the synthesis of thioethers from thiols and aldehydes formed in situ from alcohols by means of the borrowing hydrogen method (see scheme). Dehydrogenation of the alcohol gives a palladium hydride intermediate and an aldehyde. The latter reacts with a thiol through a thionium ion, which is reduced by the metal hydride to afford thioethers.
- Corma, Avelino,Navas, Javier,Rodenas, Tania,Sabater, Maria J.
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p. 17464 - 17471
(2014/01/06)
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- TAPC-catalyzed synthesis of thioethers from thiols and alcohols
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A new synthesis of thioethers is described. The reaction of aryl alcohols with aryl, heteroaryl, and alkyl thiols in the presence of TAPC as an efficient catalyst affords good to excellent yields of thioethers. Furthermore, the reaction proceeds under metal-free and solvent-free conditions thus represents an interesting complement to known methods for thioether synthesis. A plausible mechanism for this reaction is delineated. Georg Thieme Verlag Stuttgart · New York.
- Bahrami, Kiumars,Khodaei, Mohammad Mehdi,Khodadoustan, Nayere
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experimental part
p. 2206 - 2210
(2011/10/09)
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- Catalytic enantioselective oxidation of bulky alkyl aryl thioethers with H2O2 over titanium-salan catalysts
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A simple and efficient catalytic procedure for the oxidation of bulky (preferably aryl benzyl substituted) thioethers with hydrogen peroxide in good to high yields and enantioselectivities (up to 98.5%ee) is reported. The high optical yields are achieved in a tandem stereoconvergent enantioselective oxidation and kinetic resolution process. A reasonable balance between the sulfoxide yield and enantioselectivity could be found by varying the concentration and temperature. An improved synthesis of the titanium-salan catalysts for the preparation of a more stereoselective catalyst is reported.
- Bryliakov, Konstantin P.,Talsi, Evgenii P.
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supporting information; experimental part
p. 4693 - 4698
(2011/10/03)
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- Gold-catalyzed C-S bond formation from thiols
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ortho-Alkynylbenzoic acid alkyl esters act as alkylating agents of thiol derivatives with PPh3AuCl in combination with AgOTf in 1,2-dichloroethane at 80 °C. The corresponding sulfide compounds are obtained in good to excellent yields.
- Jean, Micka?l,Renault, Jacques,van de Weghe, Pierre,Asao, Naoki
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supporting information; experimental part
p. 378 - 381
(2010/03/24)
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- Synthesis of sulfides under solvent- and catalyst-free conditions
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A simple, highly efficient, and green protocol has been developed for preparation of sulfides from alkyl or aryl thiols and benzyl-, allyl-, t-butyl, and adamantyl halides under solvent- and catalyst-free conditions.
- Movassagh, Barahman,Soleiman-Beigi, Mohammad
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experimental part
p. 409 - 411
(2010/05/01)
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- Ultrasound-promoted deoxygenation of sulphoxides by samarium - NH4Cl
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Several aromatic and aliphatic sulphoxides are selectively deoxygenated to the corresponding thioethers in high to quantitative yields by samarium metal in methanolic ammonium chloride under sonication. Other functional groups such as halides, esters, ethers, nitriles, olefins and ketones are unaffected under the present reaction conditions.
- Yadav,Subba Reddy,Srinivas,Srihari
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p. 854 - 856
(2007/10/03)
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- Photochemistry of benzyl β-naphthyl sulfoxide and characterization of the β-naphthylsulfinyl radical
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Photolysis of benzyl β-naphthyl sulfoxide results mainly in α-cleavage. The isomeric sulfenic ester is the major product. Because the triplet energies of both the sulfoxide and sulfenic ester are below that of acetone, in contrast to the previously studied phenyl and tolyl cases, interpretation of sensitization experiments is straightforward. The sulfinyl radical is characterized by transient absorption and a model is proposed to account for its reactivity with nitroxide radicals.
- Guo, Yushen,Darmanyan, Alexandre P.,Jenks, William S.
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p. 8619 - 8622
(2007/10/03)
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- Oxidation potential as a measure of the reactivity of anionic nucleophiles. Behaviour of different classes of nucleophiles
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Anodic peak potentials for 42 anionic nucleophiles are reported along with the rate constants for the reactions of the anions with benzyl chloride.By comparing these rate constants with those of the reactions of outer-sphere electron-transfer reagents (radical anions), it has been demonstrated that the reactions of the anions with benzyl chloride are typical single-step SN2 reactions as opposed to a two-step process comprising dissociative single electron transfer (SET) to benzyl chloride followed by radical combination.The data suggest that very electron-rich nucleophilic anions with potentials of -1.5 to -2.2 V (and more negative) with respect to the ferrocenium/ferrocene couple might participate in a SET reaction.The 42 anions studied included representatives of four classes of nucleophiles, viz. sulfur-, carbon-, oxygen- and nitrogen-centred anions.The previously observed correlation of rate constants and anodic peak potential was again found for these anions with the most reactive species having the most negative peak potentials.Correlations by class indicate that the sensitivity of rate constants to changes in peak potential is greatest (and equivalent) for the sulfur-, carbon- and oxygen-anions and for representatives with the same peak potential, the rate constants by class follow the order sulfur > carbon > oxygen.The nitrogen nucleophiles show a significantly lower sensitivity of rate constant to changes in peak potential than do the other three classes.
- Niyazymbetov, Murat E.,Rongfeng, Zhou,Evans, Dennis H.
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p. 1957 - 1962
(2007/10/03)
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- Alkylation Reactions by Means of Alkanols and Carbon Monoxide: An Efficient Synthesis of Thioethers and of Caffeine from Theophylline
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The reaction of sodium or potassium thiolates with alkanols and carbon monoxide provides a versatile route to produce thioethers in excellent yields.By analogy, the potassium salt of theophylline suffers a nearly quantitative conversion to caffeine when heated with methanol under CO pressure.The mechanism of these alkylation reactions is discussed. - Key Words: Nucleophilic alkylation / Thioethers / Caffeine / Carbon monoxide / Alkanols
- Bott, Kaspar
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p. 1955 - 1956
(2007/10/02)
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- Cobalt carbonyl catalyzed reaction of mercaptans with Schiff bases and carbon monoxide
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Thiophenols and p-methylbenzyl mercaptan react with Schiff bases and carbon monoxide in benzene, in the presence of cobalt carbonyl, to give amides as the pricipal products.These amides arise from cleavage of the carbon-nitrogen double bond of the reactant imine.The reaction is applicable to a variety of Schiff bases (i.e. aliphatic, benzylic, aromatic).Thioesters and olefins are usually obtained as reaction by-products.
- Antebi, Shlomo,Alper, Howard
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p. 2010 - 2012
(2007/10/02)
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