- Photoredox Nickel-Catalyzed C-S Cross-Coupling: Mechanism, Kinetics, and Generalization
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Photoredox-mediated nickel-catalyzed cross-couplings have evolved as a new effective strategy to forge carbon-heteroatom bonds that are difficult to access with traditional methods. Experimental mechanistic studies are challenging because these reactions involve multiple highly reactive intermediates and perplexing reaction pathways, engendering competing, but unverified, proposals for substrate conversions. Here, we report a comprehensive mechanistic study of photoredox nickel-catalyzed C-S cross-coupling based on time-resolved transient absorption spectroscopy, Stern-Volmer quenching, and quantum yield measurements. We have (i) discovered a self-sustained productive Ni(I/III) cycle leading to a quantum yield φ > 1; (ii) found that pyridinium iodide, formed in situ, serves as the dominant quencher for the excited state photocatalyst and a critical redox mediator to facilitate the formation of the active Ni(I) catalyst; and (iii) observed critical intermediates and determined the rate constants associated with their reactivity. Not only do the findings reveal a complete reaction cycle for C-S cross-coupling, but the mechanistic insights have also allowed for the reaction efficiency to be optimized and the substrate scope to be expanded from aryl iodides to include aryl bromides, thus broadening the applicability of photoredox C-S cross-coupling chemistry.
- Qin, Yangzhong,Sun, Rui,Gianoulis, Nikolas P.,Nocera, Daniel G.
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supporting information
p. 2005 - 2015
(2021/02/06)
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- Visible-Light-Mediated Alkylation of Thiophenols via Electron Donor-Acceptor Complexes Formed between Two Reactants
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A metal-free, photocatalyst-free, photochemical system was developed for the direct alkylation of thiophenols via electron donor-acceptor (EDA) complexes (KEDA = 145 M-1) between two reactants, N-hydroxyphthalimide esters as acceptors and thiophenol anions as donors, in the presence of a tertiary amine. The EDA complexes in the reaction system have a broad range of visible-light absorption (400-650 nm) and can trigger the reaction effectively under sunlight.
- Cai, Yi-Ping,Nie, Fang-Yuan,Song, Qin-Hua
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p. 12419 - 12426
(2021/09/02)
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- Nickel-catalyzed oxidative dehydrogenative coupling of alkane with thiol for C(sp3)-S bond formation
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A nickel-catalyzed oxidative dehydrogenative coupling reaction of alkane with thiol for the construction of C(sp3)-S bond has been established, affording more than 50 alkyl thioethers. Notably, pharmaceutical and agrochemicals, such as Provigil, Chlorbenside and Pyridaben, were readily synthesized by this approach. The sterically hindered ligand BC and disulfide which was formed in situ oxidation of thiol, efficiently avoiding nickel-catalyst poisoning. A set of mechanistic experiments disclose both Ni-catalyzed and Ni-free HAA processes.
- Liu, Shengping,Jin, Shengnan,Wang, Hao,Qi, Zaojuan,Hu, Xiaoxue,Qian, Bo,Huang, Hanmin
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supporting information
(2021/03/15)
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- Ni(II) Precatalysts Enable Thioetherification of (Hetero)Aryl Halides and Tosylates and Tandem C?S/C?N Couplings
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Ni-catalyzed C?S cross-coupling reactions have received less attention compared with other C-heteroatom couplings. Most reported examples comprise the thioetherification of most reactive aryl iodides with aromatic thiols. The use of C?O electrophiles in this context is almost uncharted. Here, we describe that preformed Ni(II) precatalysts of the type NiCl(allyl)(PMe2Ar’) (Ar’=terphenyl group) efficiently couple a wide range of (hetero)aryl halides, including challenging aryl chlorides, with a variety of aromatic and aliphatic thiols. Aryl and alkenyl tosylates are also well tolerated, demonstrating, for the first time, to be competent electrophilic partners in Ni-catalyzed C?S bond formation. The chemoselective functionalization of the C?I bond in the presence of a C?Cl bond allows for designing site-selective tandem C?S/C?N couplings. The formation of the two C-heteroatom bonds takes place in a single operation and represents a rare example of dual electrophile/nucleophile chemoselective process.
- Martín, M. Trinidad,Marín, Mario,Maya, Celia,Prieto, Auxiliadora,Nicasio, M. Carmen
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supporting information
p. 12320 - 12326
(2021/08/09)
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- Visible-Light-Promoted Cross-Coupling Reactions of 4-Alkyl-1,4-dihydropyridines with Thiosulfonate or Selenium Sulfonate: A Unified Approach to Sulfides, Selenides, and Sulfoxides
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In this paper, a visible-light-promoted cross-coupling of 4-alkyl-1,4-dihydropyridines with thio-/selenium sulfonates under transition-metal-free conditions is described. This strategy features easily available substrates, mild reaction conditions, high yields, and high chemoselectivity. A novel synthetic route for the construction of a sulfide or selenide Csp3-S or Csp3-Se bond under transition-metal-free conditions without an additive oxidant or base is developed. This method is well extended to the synthesis of a class of thiolated or selenylated glycosides that has not been explored before. Sulfoxides were also successfully chemoselectively observed via a facile variation of the atmosphere under photocatalyzed conditions.
- Li, Jian,Yang, Xin-Er,Wang, Shan-Le,Zhang, Long-Long,Zhou, Xiao-Zhou,Wang, Shun-Yi,Ji, Shun-Jun
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supporting information
p. 4908 - 4913
(2020/07/13)
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- Deprotonated Salicylaldehyde as Visible Light Photocatalyst
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Salicylaldehyde is established as an efficient visible light photocatalyst for the first time. Compared to other simple aldehyde analogies, salicylaldehyde has a unique deprotonative red-shift from 324 to 417 nm and gives rise to the remarkable increase of fluorescence quantum from 0.0368 to 0.4632, thus enabling salicylaldehyde as a visible light (>400 nm) photocatalyst. The experimental investigations suggest that the reactive radical species are generated by sensitization of the substrates by the deprotonated salicylaldehyde through an energy-transfer pathway. Consequently, the C-C cleaving alkylation reactions of N-hydroxyphthalimide esters proceed smoothly in the presence of as low as 1 mol % of salicylaldehyde under the visible-light irradiation, affording desired alkylation products with up to 99% yields. Application in visible-light induced aerobic oxidation of N-alkylpyridinium salts is also reported.
- Zhuang, Yan-Jun,Qu, Jian-Ping,Kang, Yan-Biao
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p. 4386 - 4397
(2020/03/05)
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- Nickel-Catalyzed Inter- and Intramolecular Aryl Thioether Metathesis by Reversible Arylation
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A nickel-catalyzed aryl thioether metathesis has been developed to access high-value thioethers. 1,2-Bis(dicyclohexylphosphino)ethane (dcype) is essential to promote this highly functional-group-tolerant reaction. Furthermore, synthetically challenging macrocycles could be obtained in good yield in an unusual example of ring-closing metathesis that does not involve alkene bonds. In-depth organometallic studies support a reversible Ni0/NiII pathway to product formation. Overall, this work not only provides a more sustainable alternative to previous catalytic systems based on Pd, but also presents new applications and mechanistic information that are highly relevant to the further development and application of unusual single-bond metathesis reactions.
- Delcaillau, Tristan,Bismuto, Alessandro,Lian, Zhong,Morandi, Bill
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supporting information
p. 2110 - 2114
(2019/12/24)
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- Preparation method of alkyl sulfide
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The invention relates to a preparation method of alkyl sulfide. The method comprises the following steps: under the protection of nitrogen, sequentially adding transition metal, a nitrogen ligand, a cocatalyst, an oxidant, a solvent, alkane and thiophenol or mercaptan into a reaction tube, carrying out oxidative dehydrogenation coupling reaction at 80-150 DEG C, ending the reaction after 6-48 hours, evaporating the solvent to dryness, and carrying out column chromatography separation to obtain the alkyl sulfide compound. The method is simple in synthesis process, mild in reaction condition, high in yield and easy to industrialize.
- -
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Paragraph 0056
(2019/12/02)
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- CATALYTIC C-X-BOND METATHESIS THROUGH ARYLATION
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The present invention refers to a process for a catalytic aryl transfer to rearrange the backbone of aromatic C-X bonds.
- -
-
Page/Page column 9
(2018/09/28)
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- Merging Photoredox and Organometallic Catalysts in a Metal–Organic Framework Significantly Boosts Photocatalytic Activities
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Metal–organic frameworks (MOFs) have been extensively used for single-site catalysis and light harvesting, but their application in multicomponent photocatalysis is unexplored. We report here the successful incorporation of an IrIII photoredox catalyst and a NiII cross-coupling catalyst into a stable Zr12 MOF, Zr12-Ir-Ni, to efficiently catalyze C?S bond formation between various aryl iodides and thiols. The proximity of the IrIII and NiII catalytic components to each other (ca. 0.6 nm) in Zr12-Ir-Ni greatly facilitates electron and thiol radical transfers from Ir to Ni centers to reach a turnover number of 38 500, an order of magnitude higher than that of its homogeneous counterpart. This work highlights the opportunity in merging photoredox and organometallic catalysts in MOFs to effect challenging organic transformations.
- Zhu, Yuan-Yuan,Lan, Guangxu,Fan, Yingjie,Veroneau, Samuel S.,Song, Yang,Micheroni, Daniel,Lin, Wenbin
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supporting information
p. 14090 - 14094
(2018/10/15)
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- Carbon-sulphur cross coupling reactions catalyzed by nickel-based coordination polymers based on metalloligands
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This work illustrates two Ni2+ based coordination polymers (CPs, 1-Ni and 2-Ni) synthesized using two related Co3+ based metalloligands offering appended arylcarboxylate groups. The crystal structure of 1-Ni displays a porous 3D network having well-defined major and minor pores whereas 2-Ni exhibits a somewhat densely packed structure. Both CPs supported the exchange of coordinated water molecules and the inclusion of iodine within their porous structure whereas binding studies illustrated that the Ni(ii) ion in these CPs can bind thiophenol, a reagent used in the C-S cross coupling reactions. The two CPs functioned as the reusable heterogeneous catalysts for the C-S cross coupling reactions between substituted aromatic halides and thiophenol as well as cyclohexanethiol and ethanethiol.
- Kumar, Gulshan,Hussain, Firasat,Gupta, Rajeev
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p. 15023 - 15031
(2017/11/14)
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- Photoredox Mediated Nickel Catalyzed Cross-Coupling of Thiols with Aryl and Heteroaryl Iodides via Thiyl Radicals
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Ni-catalyzed cross-couplings of aryl, benzyl, and alkyl thiols with aryl and heteroaryl iodides were accomplished in the presence of an Ir-photoredox catalyst. Highly chemoselective C-S cross-coupling was achieved versus competitive C-O and C-N cross-couplings. This C-S cross-coupling method exhibits remarkable functional group tolerance, and the reactions can be carried out in the presence of molecular oxygen. Mechanistic investigations indicated that the reaction proceeded through transient Ni(I)-species and thiyl radicals. Distinct from nickel-catalyzed cross-coupling reactions involving carbon-centered radicals, control experiments and spectroscopic studies suggest that this C-S cross-coupling reaction does not involve a Ni(0)-species.
- Oderinde, Martins S.,Frenette, Mathieu,Robbins, Daniel W.,Aquila, Brian,Johannes, Jeffrey W.
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supporting information
p. 1760 - 1763
(2016/03/01)
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- Nature of the copper-oxide-mediated C-S cross-coupling reaction: Leaching of catalytically active species from the metal oxide surface
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Copper-oxide-catalyzed cross-coupling reaction is a well-known strategy in heterogeneous catalysis. A large number of applications have been developed, and catalytic cycles have been proposed based on the involvement of the copper oxide surface. In the present work, we have demonstrated that copper(I) and copper(II) oxides served as precursors in the coupling reaction between thiols and aryl halides, while catalytically active species were formed upon unusual leaching from the oxide surface. A powerful cryo-SEM technique has been utilized to characterize the solution-state catalytic system by electron microscopy. A series of different experimental methods were used to reveal the key role of copper thiolate intermediates in the studied catalytic reaction. The present study shows an example of leaching from a metal oxide surface, where the leaching process involved the formation of a metal thiolate and the release of water. A new synthetic approach was developed, and many functionalized sulfides were synthesized with yields of up to 96%, using the copper thiolate catalyst. The study suggests that metal oxides may not act as an innocent material under reaction conditions; rather, they may represent a source of reactive species for solution-state homogeneous catalysis.
- Panova, Yulia S.,Kashin, Alexey S.,Vorobev, Maxim G.,Degtyareva, Evgeniya S.,Ananikov, Valentine P.
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p. 3637 - 3643
(2016/07/06)
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- Ligand-free copper-catalyzed synthesis of asymmetrical thioethers by coupling aryl or alkyl halides using an acetyl thiourea precursor in wet polyethylene glyol (PEG 400)
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Asymmetrical diaryl or aryl alkyl thioethers can be prepared in good to excellent yields by coupling the appropriate aryl iodides and aryl or alkyl bromines using acetyl thiourea as a thiolprecursor, Cu2O as a catalyst, KOH as a base, and PEG 400-H2O as a solvent under ligand-free conditions.
- Zhang, Baohua,Shi, Lanxiang,Guo, Ruixia,Wang, Juan
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p. 561 - 566
(2015/05/20)
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- Microwave-Assisted Copper-Catalyzed Cross-Coupling Reaction of Thiols with Aryl Iodides in Water
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Microwave-promoted C-S bond formation from thiols and aryl iodides in the presence of a copper catalyst is reported. A combination of copper(II) oxide and 1,10-phenanthroline catalyzes this reaction. A variety of aryl iodides react smoothly with thiols to provide the corresponding aryl sulfides in good to excellent yields. Notably, the reactions proceed in water with a short reaction time (30 minutes). This system shows broad functional-group tolerance; amino, chloro, bromo, acetyl, and nitro groups are unaffected by the reaction conditions.
- Chen, Yi-An,Badsara, Satpal Singh,Tsai, Wan-Ting,Lee, Chin-Fa
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p. 181 - 186
(2015/05/04)
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- Metal-free preparation of cycloalkyl aryl sulfides via di-tert-butyl peroxide-promoted oxidative C(sp3)-H bond thiolation of cycloalkanes
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A concise thiolation of the C(sp3)-H bond of cycloalkanes with diaryl disulfides in the presence of the oxidant di-tert-butyl peroxide (DTBP) has been developed. This reaction, without using any metal catalyst, tolerates varieties of disulfides and cycloalkanes substrates, giving good to excellent chemical yields, and thus provides a useful approach to cycloalkyl aryl sulfides from unactivated cycloalkanes.
- Zhao, Jincan,Fang, Hong,Han, Jianlin,Pan, Yi,Li, Guigen
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p. 2719 - 2724
(2014/09/29)
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- Palladium-catalyzed thiolation of alkanes and ethers with arylsulfonyl hydrazides
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A new method for the preparation of alkyl aryl sulfides through direct oxidative thiolation of alkanes or ethers with arylsulfonyl hydrazides using di-tert-butyl peroxide (DTBP) as an oxidant catalyzed by Pd(OAc)2 has been reported. The C-H bonds in various alkanes or ethers were successfully converted into C-S bonds to yield the corresponding sulfides in moderate to good yields. the Partner Organisations 2014.
- Guo, Sheng-Rong,He, Wei-Ming,Xiang, Jian-Nan,Yuan, Yan-Qin
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p. 8578 - 8581
(2014/07/22)
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- Syntheses of sulfides and selenides through direct oxidative functionalization of C(sp3)-H bond
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A new protocol for C-S and C-Se bond formation by the direct functionalization of the C(sp3)-H bond of alkanes under metal-free conditions was developed. Using tBuOOtBu as the oxidant, the reaction of disulfides or diselenides with alkanes gave sulfides or selenides in moderate to good yields. The method was very simple and atom-economical.
- Du, Bingnan,Jin, Bo,Sun, Peipei
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supporting information
p. 3032 - 3035
(2014/06/23)
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- One-pot synthesis of aryl alkyl thioethers and diaryl disulfides using carbon disulfide as a sulfur surrogate in the presence of diethylamine catalyzed by copper(I) iodide in polyethylene glycol (PEG200)
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A copper catalyzed one-pot protocol for the preparation of aryl alkyl thioethers and diaryl disulfides using carbon disulfide as the sulfur source and diethylamine in polyethylene glycol (PEG200) is described.
- Firouzabadi, Habib,Iranpoor, Nasser,Samadi, Arash
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p. 1212 - 1217
(2014/02/14)
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- A well-defined (POCOP)Rh catalyst for the coupling of aryl halides with thiols
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This article describes a well-defined pincer-Rh catalyst for C-S cross-coupling reactions. (POCOP)Rh(H)(Cl) serves as an active precatalyst for the coupling of aryl chlorides and bromides with aryl and alkyl thiols under reasonable conditions (3% mol cat., 110 °C, 2-24 h, >90% yield). For select substrates, >90% yields were obtained with catalyst loading as low as 0.1%. Key mechanistic intermediates have been isolated and fully characterized, including (POCOP)Rh(Ph)(SPh) (6a) and (POCOP)Rh(SPh2) (6b). The aryl/bis(phosphinite) (POCOP)Rh system has been shown to favor aryl thiolate reductive elimination at elevated temperatures and in some cases at room temperature, compared with the analogous diarylamido/bis(phosphine) (PNP)Rh pincer system. Concerted reductive elimination has been studied with 6a directly and in the presence of aryl bromide and aryl chloride traps. This investigation demonstrates a clear rate dependence on aryl chloride concentration during catalysis, a dependence that is absent when using aryl bromides. The rate of catalysis is dramatically reduced or brought to zero for ortho-tolyl halides, which can be traced to slower C-S coupling and slower carbon-halogen oxidative addition for ortho-substituted aryls. The influence of the sterics in the thiol component is less straightforward. The S-H oxidative addition product (POCOP)Rh(H)(SPh) (16) has been fully characterized and its reactivity has been examined, resulting in the isolation of the sodium-thiolate adduct (POCOP)Rh(NaSPh) (19). The solid-state structure of 19 shows Na interactions not only with sulfur, but also with a neighboring Rh and the chelating aryl carbon of the pincer framework. The reactivity of 16 and 19 indicates that these potential side products should not hinder catalysis.
- Timpa, Samuel D.,Pell, Christopher J.,Ozerov, Oleg V.
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supporting information
p. 14772 - 14779
(2015/01/16)
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- Carbon-sulfur bond formation catalyzed by [Pd(IPr*OMe) (cin)Cl] (cin = cinnamyl)
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The newly prepared complex [Pd(IPr*OMe)(cin)(Cl)] provides high catalytic activity for carbon-sulfur cross-coupling reactions. Nonactivated and deactivated aryl halides were successfully coupled with a large variety of aryl- and alkylthiols using this well-defined palladium N-heterocyclic carbene (NHC) complex.
- Bastug, Gulluzar,Nolan, Steven P.
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supporting information
p. 9303 - 9308
(2013/10/08)
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- Manganese-catalyzed cross-coupling of thiols with aryl iodides
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A manganese-catalyzed cross-coupling reaction of thiols with aryl iodides, furnishing aryl thioethers in good to excellent yields has been reported; the system shows good functional group tolerance and enables the sterically demanding aryl iodides to couple with thiols. Coming up for ArI: A manganese-catalyzed cross-coupling reaction of thiols with aryl iodides that furnishes aryl thioethers in good to excellent yields has been reported. Functional groups such as unprotected alcohols and chloro substituents are tolerated under these reaction conditions. Moreover, this catalytic system enables the sterically demanding aryl iodides to couple with thiols (see scheme; R=aryl or alkyl).
- Liu, Tsung-Jui,Yi, Chih-Lun,Chan, Chien-Ching,Lee, Chin-Fa
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p. 1029 - 1034
(2013/08/25)
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- Copper oxide nanoparticles supported on graphene oxide-Catalyzed S-arylation: An efficient and ligand-free synthesis of aryl sulfides
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Copper oxide nanoparticles that are supported on graphene oxide as a catalytic system have been utilized for ligand-free and solvent-free C-S cross-coupling reactions with weak bases such as tri- ethylamine. Symmetrical/unsymmetrical aryl sulfides have been synthesized by the coupling of different aryl halides with aromatic as well as aliphatic sulfides. Surprisingly, aryl chlorides also well reacted with different types of sulfides in the presence of dimethyl sulfoxide and cesium carbonate. Besides, this catalytic system is suitable for the synthesis of phenothiazines via cascade C-S and C-N cross-coupling of ortho-dihalides and ortho-aminobenzothiazoles. In addition, this alternative approach is extremely useful for the synthesis of a variety of symmetrical diaryl sulfides by using thiourea as a sulfur source that is devoid of the foul smell of thiols. Indeed, the calculated E-factor value of our present protocol is 2.52. Furthermore, this protocol is particularly attractive as an environmentally benign and practical method for the synthesis of different aryl sulfides. Moreover, the heterogeneous catalytic system described in this process represents not only a greener approach but retains its significant activity for up to six catalytic cycles.
- Kamal, Ahmed,Srinivasulu, Vunnam,Murty,Shankaraiah, Nagula,Nagesh, Narayana,Reddy, T. Srinivasa,Subba Rao
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p. 2297 - 2307
(2013/10/01)
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- Synthesis of aryl thioethers through the N -chlorosuccinimide-promoted cross-coupling reaction of thiols with Grignard reagents
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A convenient one-pot approach for the synthesis of aryl sulfides through the coupling of thiols with Grignard reagents in the presence of N-chlorosuccinimide is described. The sulfenylchlorides were formed when thiols were treated with N-chlorosuccinimide, and the resulting sulfenylchlorides were then directly reacted with Grignard reagents to provide aryl sulfides in good to excellent yields under mild reaction conditions. Functional groups including ester, fluoro, and chloro are tolerated by the reaction conditions employed. It is important to note that this method has a short reaction time (30 min in total) and represents an alternative approach for the synthesis of aryl sulfides over the existing protocols.
- Cheng, Jun-Hao,Ramesh, Chintakunta,Kao, Hsin-Lun,Wang, Yu-Jen,Chan, Chien-Ching,Lee, Chin-Fa
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p. 10369 - 10374
(2013/01/15)
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- A general rhodium-catalyzed cross-coupling reaction of thiols with aryl iodides
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The general procedure for the rhodium-catalyzed cross-coupling of thiols with aryl iodides is described. The catalytic system consists of 5 mol % of [RhCl(cod)]2 and 10 mol % of PPh3 as a ligand. A variety of aryl iodides reacted with thiols, giving aryl thioethers in good to excellent yields. It is important to note that the deactivated aryl iodides such as 4-iodoanisole is worked smoothly to provide the corresponding aryl thioethers in excellent yields. Functional groups such as free-amines, chloro, are all tolerated under the employed reaction conditions.
- Lai, Chih-Shin,Kao, Hsin-Lun,Wang, Yan-Jhang,Lee, Chin-Fa
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supporting information; experimental part
p. 4365 - 4367
(2012/09/22)
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- An efficient copper-catalyzed cross-coupling reaction of thiols with aryl iodides
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Commercially available Cu2O powder is a very reactive catalyst for the coupling of thiols to aryl iodides. A variety of functional groups including esters, unprotected amines, alcohols, and heterocycles tolerate the reaction conditions. Moreover, di-ortho-substituted aryl iodides with sterically demanding substrates were also coupled to give the desired aryl thioethers in good to excellent yields. Copyright
- Kao, Hsin-Lun,Chen, Chin-Keng,Wang, Yu-Jen,Lee, Chin-Fa
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experimental part
p. 1776 - 1781
(2011/05/03)
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- Nano-CuFe2O4 as a magnetically separable and reusable catalyst for the synthesis of diaryl/aryl alkyl sulfides via cross-coupling process under ligand-free conditions
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An efficient protocol was developed for the CuFe2O4 nanopowder-catalyzed aryl-sulfur bond formation between aryl halide and thiol/disulfide. A variety of aryl sulfides were synthesized in impressive yields with good chemoselectivity and functional group tolerance in the presence of a catalytic amount of CuFe2O4, Cs2CO 3 as base, in nitrogen atmosphere, under ligand-free conditions, in DMSO as solvent at 100 °C. The catalyst is air-stable, inexpensive, magnetically separable and recyclable up to four cycles.
- Swapna, Kokkirala,Murthy, Sabbavarapu Narayana,Jyothi, Mocharla Tarani,Nageswar, Yadavalli Venkata Durga
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experimental part
p. 5989 - 5996
(2011/10/08)
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- One-pot thioetherification of aryl halides using thiourea and alkyl bromides catalyzed by copper(I) iodide free from foul-smelling thiols in wet polyethylene glycol (PEG 200)
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In this article, we have developed a new protocol for the thioarylation of structurally diverse alkyl bromides such as benzyl, cinnamyl, n-octyl, cyclohexyl, cyclopentyl, and tert-butyl bromides with aryl iodides, bromides and an activated chloride using thiourea catalyzed by copper(I) iodide in wet polyethylene glycol (PEG 200) as an eco-friendly medium in the presence of potassium carbonate at 80 and 100°C under an inert atmosphere. The process is free from foul-smelling thiols which makes this method more practical for the thioetherification of aryl halides. Another important feature of this method is the variety of alkyl bromides which are commercially available for the in situ generation of thiolate ions with respect to the existing protocols in which the less commercially available thiols are directly used for the preparation of arylthio ethers.
- Firouzabadi, Habib,Gholinejad, Mohammad,Iranpoor, Nasser
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supporting information; experimental part
p. 119 - 124
(2015/03/06)
-
- Recyclable iron/graphite catalyst for c-s cross coupling of thiols with aryl halides under ligand-free conditions
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A recyclable iron/graphite (Fe/Cg) catalyst for the efficient C-S cross-coupling of various iodoarenes with aromatic/aliphatic thiols has been developed under ligand-free conditions (26 examples, up to 99% yield). The catalyst can be easily recovered and recycled up to seven cycles without loss of activity. Georg Thieme Verlag Stuttgart.
- Akkilagunta, Vijay Kumar,Reddy, Vutukuri Prakash,Rao, Kakulapati Rama
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supporting information; experimental part
p. 1260 - 1264
(2010/07/05)
-
- MnCl2·4H2O-catalyzed potential protocol for the synthesis of aryl/vinyl sulfides
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MnCl2 · 4H2O is described as an efficient catalytic system for the cross coupling of aryl/vinyl halides with thiols using KOH as base and DMSO as solvent. By using this new catalytic system various aryl/vinyl sulfides were synthesize
- Bandaru, Madhav,Sabbavarpu, Narayana Murthy,Katla, Ramesh,Yadavalli, Venkata Durga Nageswar
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supporting information; experimental part
p. 1149 - 1151
(2011/02/28)
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- An efficient, mild and intermolecular ullmann-type synthesis of thioethers catalyzed by a diol-copper(I) complex
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A wide range of diaryl sulfides and aryl alkyl sulfides are synthesized under mild reaction conditions from the corresponding aryl iodides and aromatic/aliphatic thiols through Ullmann-type intermolecular coupling reactions in the presence of catalytic amount of easily available novel trans-9,10-dihydro-9,10-ethanoanthracene-11,12-dimethanol-copper(I) bromide complex at 82 C. The catalytic system is not only capable of coupling electron-withdrawing and electron-releasing substituent-containing substrates, but also tolerates a broad range of functional groups including heteroatom-containing aryl iodides and thiols.
- Prasad,Sekar, Govindasamy
-
experimental part
p. 79 - 84
(2010/06/15)
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- A general, efficient, and functional-group-tolerant catalyst system for the palladium-catalyzed thioetherification of aryl bromides and iodides
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The cross-coupling reaction of aryl bromides and iodides with aliphatic and aromatic thiols catalyzed by palladium complexes of the bisphosphine ligand CyPF-tBu (1) is reported. Reactions occur in excellent yields, broad scope, high tolerance of functional groups, and with turnover numbers that exceed those of previous catalysts by 2 or 3 orders of magnitude. These couplings of bromo- and iodoarenes are more efficient than the corresponding reactions of chloroarenes and could be conducted with less catalyst loading and/or milder reaction conditions. Consequently, limitations regarding scope and functional group tolerance previously reported in the coupling of aryl chlorides are now overcome.
- Fernandez-Rodriguez, Manuel A.,Hartwig, John F.
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experimental part
p. 1664 - 1672
(2009/07/17)
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- Nano indium oxide as a recyclable catalyst for C-S cross-coupling of thiols with aryl halides under ligand free conditions
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An efficient ligand-free C-S cross-coupling of aryl halides with aromatic/alkyl thiols has been developed using a catalytic amount of nanocrystalline indium oxide as a recyclable catalyst with KOH as the base in DMSO at 135 °C. A variety of aryl sulfides can be synthesized in excellent yields utilizing this protocol.
- Reddy, Vutukuri Prakash,Kumar, Akkilagunta Vijay,Swapna, Kokkirala,Rao, Kakulapati Rama
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supporting information; experimental part
p. 1697 - 1700
(2009/09/06)
-
- Indium-catalyzed C-S cross-coupling of aryl halides with thiols
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Indium-catalyzed C-S cross-coupling of aromatic and alkane thiols with aryl halides proceeds smoothly in the presence of In(OTf)3 (10 mol %), TMEDA (20 mol %), and KOH as a base in DMSO at 135 °C. When this protocol was utilized, a variety of thiols could be cross-coupled with aryl halides to afford the corresponding aryl sulfides in good to excellent yields.
- Reddy, V. Prakash,Swapna,Kumar, A. Vijay,Rao, K. Rama
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supporting information; experimental part
p. 3189 - 3191
(2009/08/08)
-
- Lanthanum(III) oxide as a recyclable catalyst for the synthesis of diaryl sulfides and diaryl selenides
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La2O3 as a new and efficient recyclable catalyst in coupling various aryl halides with aromatic/alkyl thiols and diphenyl diselenide in combination with KOH as a base and DMEDA as a ligand in DMSO at 110 °C is reported.
- Murthy, Sabbavarapu Narayana,Madhav, Bandaru,Reddy, Vutukuri Prakash,Nageswar, Yadavalli Venkata Durga
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supporting information; experimental part
p. 5902 - 5905
(2010/03/02)
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- CATALYSTS FOR ARYL SULFIDE SYNTHESIS AND METHOD OF PRODUCING ARYL SULFIDES
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The present invention relates to the formation of aryl sulfides and aryl thiols from aryl halides and thiols, thiolates or thiolate equivalents. The present invention provides a catalyst for the coupling of aryl halides with alkyl or aryl thiols or a hydrogen sulfide equivalent to form aryl alkyl, aryl silyl or diaryl sulfides. The reaction encompasses bromoarenes and other similar compounds containing leaving groups as well as nitrile, ester, keto, free hydroxyl, free amino, free carboxylic acid and other common functionalities. The invention can be used to prepare pharmaceutical compounds, especially including their intermediates, agricultural agents and aryl sulfide polymers.
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Page/Page column 20; 29; 34-35; 48
(2008/06/13)
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- Cobalt-catalyzed aryl-sulfur bond formation
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A new cobalt-catalyzed coupling of aryl halides with thiophenols and alkanethiols is reported. A variety of aryl sulfides can be prepared in excellent yields under mild reaction conditions using 1-2 mol % of Col2(dppe) and Zn. This new cobalt-catalyzed coupling represents an interesting addition to previously known methods to synthesize thioethers.
- Wong, Ying-Chieh,Jayanth, Thiruvellore Thatai,Cheng, Chien-Hong
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p. 5613 - 5616
(2007/10/03)
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- A general and long-lived catalyst for the palladium-catalyzed coupling of aryl halides with thiols
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A general catalytic system for the coupling of aryl halides and sulfonates with thiols based on the use of the CyPF-t-Bu ligand (1) is reported. The reactions catalyzed by complexes of 1 occur in excellent yields with broad scope and exhibit extraordinary turnover numbers and high tolerance of functional groups. Turnover numbers usually exceed those of previous catalysts by 2 or 3 orders of magnitude. In addition, the reactions of aryl tosylates with alkane thiols to form aryl sulfides are reported for the first time. Finally, the synthesis of a diarylsulfide from two bromoarenes was accomplished using a hydrogen sulfide surrogate. Copyright
- Fernandez-Rodriguez, Manuel A.,Shen, Qilong,Hartwig, John F.
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p. 2180 - 2181
(2007/10/03)
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- Highly efficient and functional-group-tolerant catalysts for the palladium-catalyzed coupling of aryl chlorides with thiols
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The cross-coupling reaction of aryl chlorides with aliphatic and aromatic thiols catalyzed by palladium complexes of the strongly binding bisphosphine CyPF-tBu ligand (1) is reported. Most of the reactions catalyzed by complexes of ligand 1 occur with turnover numbers that exceed those of previous catalysts by two orders of magnitude. The reactions occur with excellent yields, broad scope and high tolerance of functional groups. Coupling of aryl halides with thiols in the presence of low loadings of catalysts derived from other Josiphos type ligands, as well as ligands of other structural types, are also described.
- Fernandez-Rodriguez, Manuel A.,Shen, Qilong,Hartwig, John F.
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p. 7782 - 7796
(2007/10/03)
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- Copper-mediated cross-coupling of aryl boronic acids and alkyl thiols
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matrix presented The cross-coupling of aryl boronic acids and alkanethiols mediated by copper(II) acetate and pyridine in anhydrous dimethylformamide affords aryl alkyl sulfides in good yield with a wide variety of substituted aryl boronic acids. The method is applicable to the synthesis of aryl sulfides of cysteine.
- Herradura, Prudencio S.,Pendola, Kathleen A.,Guy, R. Kiplin
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p. 2019 - 2022
(2007/10/03)
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- NONCONVENTIONAL FRIEDEL-CRAFTS CHEMISTRY III. ON THE REGIOSPECIFIC SYNTHESIS OF SPIRO-4'-ONE DERIVATIVES
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The rection of 1-oxa-4-thiaspirononan-2-one (4) and/or 1-oxa-4-thiaspirodecan-2-one (5) with arenes (6) under the catalytic action of aluminum chloride afforded in all cases spiro-4'-ones (7a - g and 8a - g), -acetic acid, (9a - g and 10a - g), cycloalkylthioacetic acids, (11 and 20) aryl cycloalkyl sulfides, (14 and 23) diarylsulfides (15), diaryl disulfides and dicycloalkyl disulfides (13 and 22).The mechanisms of these reactions are discussed.Key words: Spiroisothiochroman-4-ones; Friedel-Crafts reactions.
- El-Zohry, Maher F.
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p. 311 - 320
(2007/10/02)
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