- Palladium-catalysed thioetherification of aryl and alkenyl iodides using 1,3,5-trithiane as sulfur source
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Thioetherification reaction of aryl iodides catalysed by palladium(II) complexes in the presence of 1,3,5-trithiane as sulphur source is reported. The paper presents the first homogeneous catalytic application of 1,3,5-trithiane in synthesis. Detailed optimization steps, the frames of the novel reaction are described, as well as the limitations and the substrate scope are also demonstrated. Moderate to good thioether yields were achieved in the presence of various substituted iodobenzenes and some alkenyl iodides, using palladium-xantphos catalyst system. Competitive reactions in the presence of mixed substrates were also performed and mechanistic considerations were assumed.
- Kollár, László,Rajat Rao, Yalamarti Venkat,Zugó, Alexandra,Pongrácz, Péter
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- Dimsyl Anion Enables Visible-Light-Promoted Charge Transfer in Cross-Coupling Reactions of Aryl Halides
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A methodology is reported for visible-light-promoted synthesis of unsymmetrical chalcogenides enabled by dimsyl anion in the absence of transition-metals or photoredox catalysts. The cross-coupling reaction between aryl halides and diaryl dichalcogenides proceeds with electron-rich, electron-poor, and heteroaromatic moieties. Mechanistic investigations using UV-Vis spectroscopy, time-dependent density functional theory (TD-DFT) calculations, and control reactions suggest that dimsyl anion forms an electron-donor-acceptor (EDA) complex capable of absorbing blue light, leading to a charge transfer responsible for generation of aryl radicals from aryl halides. This previously unreported mechanistic pathway may be applied to other light-induced transformations performed in DMSO in the presence of bases and aryl halides.
- Pan, Lei,Cooke, Maria Victoria,Spencer, Amara,Laulhé, Sébastien
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p. 420 - 425
(2021/11/01)
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- Rh(I)-Catalyzed Intramolecular Decarbonylation of Thioesters
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Decarbonylative synthesis of thioethers from thioesters proceeds in the presence of a catalytic amount of [Rh(cod)Cl]2 (2 mol %). The protocol represents the first Rh-catalyzed decarbonylative thioetherification of thioesters to yield valuable thioethers. Notable features include the absence of phosphine ligands, inorganic bases, and other additives and excellent group tolerance to aryl chlorides and bromides that are problematic using other metals to promote decarbonylation. Gram scale synthesis, late-stage pharmaceutical derivatization, and orthogonal site-selective cross-couplings by C-S/C-Br cleavage are reported.
- Cao, Han,Liu, Xuejing,Bie, Fusheng,Shi, Yijun,Han, Ying,Yan, Peng,Szostak, Michal,Liu, Chengwei
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p. 10829 - 10837
(2021/07/28)
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- Pd-Catalyzed Double-Decarbonylative Aryl Sulfide Synthesis through Aryl Exchange between Amides and Thioesters
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We report the palladium-catalyzed double-decarbonylative synthesis of aryl thioethers by an aryl exchange reaction between amides and thioesters. In this method, amides serve as aryl donors and thioesters are sulfide donors, enabling the synthesis of valuable aryl sulfides. The use of Pd/Xantphos without any additives has been identified as the catalytic system promoting the aryl exchange by C(O)-N/C(O)-S cleavages. The method is amenable to a wide variety of amides and sulfides.
- Bie, Fusheng,Cao, Han,Liu, Chengwei,Liu, Xuejing,Shi, Yijun,Szostak, Michal,Zhou, Tongliang
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p. 8098 - 8103
(2021/10/25)
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- Preparation of Recyclable and Versatile Porous Poly(aryl thioether)s by Reversible Pd-Catalyzed C–S/C–S Metathesis
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Porous organic materials (polymers and COFs) have shown a number of promising properties; however, the lability of their linkages often limits their robustness and can hamper downstream industrial application. Inspired by the outstanding chemical, mechanical, and thermal resistance of the 1D polymer poly(phenylene sulfide) (PPS), we have designed a new family of porous poly(aryl thioether)s, synthesized via a mild Pd-catalyzed C–S/C–S metathesis-based method, that merges the attractive features common to porous polymers and PPS in a single material. In addition, the method is highly modular, allowing to easily introduce application-oriented functionalities in the materials for a series of environmentally relevant applications including metal capture, metal sensing, and heterogeneous catalysis. Moreover, despite their extreme chemical resistance, the polymers can be easily recycled to recover the original monomers, offering an attractive perspective for their sustainable use. In a broader context, these results clearly demonstrate the untapped potential of emerging single-bond metathesis reactions in the preparation of new, recyclable materials.
- Morandi, Bill,Rivero-Crespo, Miguel A.,Toupalas, Georgios
-
supporting information
p. 21331 - 21339
(2021/12/17)
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- Aryl thioether compound and preparation method thereof
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The invention discloses an aryl thioether compound and a synthesis method thereof, wherein an aryl carboxylic acid and a mercaptan (phenol) are used as main raw materials, and a nickel catalyst is prepared. Under the action of the phosphine ligand and the additive, the aryl carboxylic acid and the thiol (phenol) react in an organic solvent, and after the reaction is finished, the corresponding aryl thioether is obtained. The method has the advantages of low cost, high yield, simple and convenient operation, no pollution and the like, and has potential industrial application prospects. The method provides a cheap and green way for preparation of aryl thioether compounds.
- -
-
Paragraph 0018
(2021/11/27)
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- Chan-Lam-Type C-S Coupling Reaction by Sodium Aryl Sulfinates and Organoboron Compounds
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A Chan-Lam-Type C-S coupling reaction using sodium aryl sulfinates has been developed to provide diaryl thioethers in up to 92% yields in the presence of a copper catalyst and potassium sulfite. Both electron-rich and electron-poor sodium aryl sulfinates and diverse organoboron compounds were tolerated for the synthesis of aryl and heteroaryl thioethers and dithioethers. The mechanistic study suggested that potassium sulfite was involved in the deoxygenation of sulfinate through a radical process.
- Lam, Long Yin,Ma, Cong
-
supporting information
p. 6164 - 6168
(2021/08/16)
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- 2-Sulfoximidoyl acetic acids from multicomponent petasis reactions and their use as building blocks in syntheses of sulfoximine benzodiazepine analogues
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Upon application of a multicomponent Petasis reaction, a broad range of NH-sulfoximines and boronic acids react with glyoxalic acid to afford the corresponding 2-substituted acetic acids with N-bound sulfoximidoyl groups. The protocol features excellent y
- Hommelsheim, Renè,Nú?ez Ponce, Heliana Michaela,Truong, Khai-Nghi,Rissanen, Kari,Bolm, Carsten
-
supporting information
p. 3415 - 3420
(2021/05/04)
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- A Robust Pd-Catalyzed C-S Cross-Coupling Process Enabled by Ball-Milling
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An operationally simple mechanochemical C-S coupling of aryl halides with thiols has been developed. The reaction process operates under benchtop conditions without the requirement for a (dry) solvent, an inert atmosphere, or catalyst preactivation. The reaction is finished within 3 h. The reaction is demonstrated across a broad range of substrates; the inclusion of zinc metal has been found to be critical in some instances, especially for coupling of alkyl thiols.
- Browne, Duncan L.,Jones, Andrew C.,Nicholson, William I.,Smallman, Harry R.
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p. 7433 - 7438
(2020/10/09)
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- Ligand-Free Copper(I)-Mediated Cross-Coupling Reactions of Organostannanes with Sulfur Electrophiles
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The synthesis of aryl thioether through the cross-coupling of C-S bond is a highly attractive area of research due to the prevalence of aryl thioether in bioactive natural products, functional materials, agrochemicals, and pharmaceutically active compound
- Zhu, Feng,Chen, Zhenhao,Walczak, MacIej A.
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p. 11942 - 11951
(2020/10/12)
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- DABCO-promoted Diaryl Thioether Formation by Metal-catalyzed Coupling of Sodium Sulfinates and Aryl Iodides
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A scalable catalytic synthesis method using commodity chemicals for constructing diaryl thioethers directly from sodium arylsulfinates and iodoarenes is reported in this study. In the presence of CuO or other copper salts such as Cu(OAc)2 as well as palladium catalysts, DABCO demonstrated to be essential to promote this transformation. Various iodoarenes and aryl sulfinates were examined and demonstrated the viability of this method. The mechanistic study showed that radical reactions occurred, while DABCO N-oxide radical can be observed by mass spectrometry. A plausible catalytic mechanism involving DABCO is also discussed, suggesting synergistic reduction of sulfinate by Cu(II) and DABCO is the key step of this coupling reaction. (Figure presented.).
- Liu, Yanpeng,Lam, Long Yin,Ye, Jiqing,Blanchard, Nicolas,Ma, Cong
-
supporting information
p. 2326 - 2331
(2020/05/05)
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- A Unified and Practical Method for Carbon–Heteroatom Cross-Coupling using Nickel/Photo Dual Catalysis
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While carbon–heteroatom cross-coupling reactions have been extensively studied, many methods are specific and limited to a particular set of substrates or functional groups. Reported here is a general method that allows for C?O, C?N and C?S cross-coupling reactions under one general set of conditions. We propose that an energy transfer pathway, in which an iridium photosensitizer produces an excited nickel(II) complex, is responsible for the key reductive elimination step that couples aryl bromides, iodides, and chlorides to 1° and 2° alcohols, amines, thiols, carbamates, and sulfonamides, and is amenable to scale up via a flow apparatus.
- Escobar, Randolph A.,Johannes, Jeffrey W.
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supporting information
(2020/04/17)
-
- Forging C-S Bonds through Nickel-Catalyzed Aryl Anhydrides with Thiophenols: Decarbonylation or Decarbonylation Accompanied by Decarboxylation
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A nickel-catalyzed decarbonylation or decarbonylation accompanied by decarboxylation cross-coupling reaction of aryl anhydrides with thiophenols as coupling partners was disclosed. This method is promoted by a commercially available, moisture-stable, and inexpensive nickel(II) precatalyst. The process can tolerate a variety of functional groups using ubiquitous aryl anhydrides as cross-coupling precursors to produce thioethers in moderate to excellent yields.
- Zhou, Jing-Ya,Tao, Shou-Wei,Liu, Rui-Qing,Zhu, Yong-Ming
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p. 11891 - 11901
(2019/10/11)
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- Decarbonylative thioetherification by nickel catalysis using air- and moisture-stable nickel precatalysts
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A general, highly selective method for decarbonylative thioetherification of aryl thioesters by C-S cleavage is reported. These reactions are promoted by a commercially-available, user-friendly, inexpensive, air- and moisture-stable nickel precatalyst. The process occurs with broad functional group tolerance, including free anilines, cyanides, ketones, halides and aryl esters, to efficiently generate thioethers using ubiquitous carboxylic acids as ultimate cross-coupling precursors (cf. conventional aryl halides or pseudohalides). Selectivity studies and site-selective orthogonal cross-coupling/thioetherification are described. This thioester activation/coupling has been highlighted in the expedient synthesis of biorelevant drug analogue. In light of the synthetic utility of thioethers and Ni(ii) precatalysts, we anticipate that this user-friendly method will be of broad interest.
- Liu, Chengwei,Szostak, Michal
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p. 2130 - 2133
(2018/03/06)
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- Palladium- and Nickel-Catalyzed Decarbonylative C-S Coupling to Convert Thioesters to Thioethers
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This Letter describes the development of a catalytic decarbonylative C-S coupling reaction that transforms thioesters into thioethers. Both Pd- and Ni-based catalysts are developed and applied to the construction of diaryl, aryl alkyl, and heterocycle-containing thioethers.
- Ichiishi, Naoko,Malapit, Christian A.,Wo?niak, Aukasz,Sanford, Melanie S.
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supporting information
p. 44 - 47
(2018/01/17)
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- Aryl sulfoxide, thioether compound, synthesis method and application thereof
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The invention discloses a method for selective synthesis of an aryl sulfoxide compound (III) and an aryl thioether compound (IV). According to the invention, in a reactive solvent, an aryl high iodinesalt is adopted as the reaction raw material, aryl/alkyl thiosulfate is taken as the vulcanizing reagent, under the catalysis of visible light and a photosensitive reagent, and under the action of lewis acid and alkali, when the reaction atmosphere is nitrogen, the thioether compound (IV) can be generated, and when the reaction atmosphere is air, the sulfoxide compound (III) can be generated. Thesynthesis method provided by the invention has the advantages of easily available and cheap raw materials, simple reaction operation, mild and environment-friendly reaction conditions, high yield, and excellent functional group tolerance. The invention also discloses the new aryl sulfoxide compound (III) and aryl thioether compound (IV), also successfully realizes later modification of drugs andsugar, and realizes the formal synthesis of some drugs, and provides an efficient method for selective construction of thioether and sulfoxide compounds.
- -
-
Paragraph 0253-0256
(2018/04/21)
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- Nickel Phosphite/Phosphine-Catalyzed C-S Cross-Coupling of Aryl Chlorides and Thiols
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A method for the coupling of aryl chlorides and thiophenols using an air-stable nickel(0) catalyst is described. This thioetherification procedure can be effectively applied to a range of electronically diverse aryl/heteroaryl chlorides without more expensive metal catalysts such as palladium, iridium, or ruthenium. This investigation also illustrates both, a variety of thiol coupling partners and, in certain cases, the use of Cs2CO3.
- Jones, Kieran D.,Power, Dennis J.,Bierer, Donald,Gericke, Kersten M.,Stewart, Scott G.
-
supporting information
p. 208 - 211
(2018/01/17)
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- Merging Photoredox and Organometallic Catalysts in a Metal–Organic Framework Significantly Boosts Photocatalytic Activities
-
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
-
supporting information
p. 14090 - 14094
(2018/10/15)
-
- Controllable Sulfoxidation and Sulfenylation with Organic Thiosulfate Salts via Dual Electron- and Energy-Transfer Photocatalysis
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Sulfoxides and sulfides are two important functional groups in organic molecules, containing different valence states of sulfur. Both sulfoxidation and sulfenylation with common sulfurating reagents were successfully tuned via a facile variation of the atmosphere under photocatalyzed conditions. The sulfoxidation and sulfenylation transformations involved tandem electron-/energy-transfer and single-electron-transfer processes, respectively. Late-stage sulfoxidation for pharmaceuticals and sugar derivatives was established to be highly compatible. Divergent formal syntheses of sulfoxide/sulfide-containing marketed pharmaceuticals were switchably implemented. Gram-scale operations further demonstrated the practicability of the protocol.
- Li, Yiming,Wang, Ming,Jiang, Xuefeng
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p. 7587 - 7592
(2017/11/10)
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- Photoredox mediated nickel catalyzed C(sp3)-H thiocarbonylation of ethers
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The first direct C(sp3)-H thiocarbonylation reaction is achieved by visible light photoredox/Ni dual catalysis. The thioester group of thiobenzoate is transferred to the α-oxy carbon of various cyclic/acyclic ethers, which is the opposite to the commonly expected chemical reactivity involving acyl group transfer via the weaker C(acyl)-S activation. Through mechanistic studies, we proposed that the reaction is initiated by photocatalytic reduction and fragmentation of the thioester into an acyl radical and a thiolate. A nickel complex binds to the thiolate and induces the decarbonylation of the acyl radical to form an aryl radical, which abstracts hydrogen from the α-oxy carbon of the ether. The resulting α-oxy C(sp3) centered radical re-binds to the (RS)(CO)Ni complex, which undergoes CO migratory insertion and reductive elimination to give the desired thioester product.
- Kang, Byungjoon,Hong, Soon Hyeok
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p. 6613 - 6618
(2017/08/29)
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- CuI/Oxalic Diamide-Catalyzed Cross-Coupling of Thiols with Aryl Bromides and Chlorides
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We report a general copper-catalyzed cross-coupling of thiols with aryl halides by using N-aryl-N′-alkyl oxalic diamide (L3) or N,N′-dialkyl oxalic diamide (L5) as the ligand. Both aryl and alkyl thiols can be coupled with unactivated aryl bromides and chlorides to give the desired products in good yields. Furthermore, this system features a broad substrate scope and good tolerance of functional groups. Importantly, the oxalic diamides are stable and can be prepared easily from commercially available and cheap starting materials.
- Chen, Chia-Wei,Chen, Yi-Ling,Reddy, Daggula Mallikarjuna,Du, Kai,Li, Chao-En,Shih, Bo-Hao,Xue, Yung-Jing,Lee, Chin-Fa
-
supporting information
p. 10087 - 10091
(2017/08/01)
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- Cross C-S coupling reaction catalyzed by copper(i) N-heterocyclic carbene complexes
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Copper(i) N-heterocyclic carbene has a good activity towards aryl halides and was used as a model complex to study the catalytic cycle of Cu(i) to catalyze the cross C-S coupling reaction because the N-heterocyclic carbene has a strong electron donating property, and ligand dissociation can be avoided. Free radical scavenger cumene does not retard the yield of the reaction indicating that the catalytic reaction goes through a non free radical path. Switching the solvent from toluene to DMF lowered the yield of the reaction. DFT calculation shows that the activation of aryl halide is the rate determining step, and the activation energy is higher for the reaction in DMF than in toluene. A plausible catalytic cycle is proposed with the support of DFT calculation.
- Huang, Wei-Kai,Chen, Wei-Ting,Hsu, I.-Jui,Han, Chien-Chung,Shyu, Shin-Guang
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p. 4912 - 4920
(2017/02/05)
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- A highly efficient heterogeneous copper-catalyzed Chan-Lam coupling between thiols and arylboronic acids leading to diaryl sulfides under mild conditions
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The heterogeneous Chan-Lam coupling reaction between thiols and arylboronic acids was achieved in EtOH at room temperature in the presence of 5 mol % of MCM-41-immobilized 1,10-phenanthroline-copper(II) complex [MCM-41-1,10-Phen-CuSO4] with n-Bu4NOH (40% aq) as base under O2 atmosphere, yielding a variety of unsymmetrical diaryl sulfides in good to excellent yields under mild and green conditions. The new heterogeneous copper complex can easily be prepared by a simple procedure from commercially readily available and inexpensive reagents, and recovered by a simple filtration of the reaction solution and recycled for at least eight times without significant loss of catalytic activity.
- Lin, Yang,Cai, Mingzhong,Fang, Zhiqiang,Zhao, Hong
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p. 3335 - 3343
(2016/05/19)
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- Ascorbic Acid Promoted Metal-Free Synthesis of Aryl Sulfides with Anilines Nitrosated in Situ by tert -Butyl Nitrite
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A mild, metal-free synthesis of aryl sulfides has been disclosed. Aryl diazonium ion was generated by the in situ nitrosation of aniline, and it was reduced by ascorbic acid (vitamin C) to form aryl radical, which underwent a thiolation with disulfide to yield aryl sulfide. The reaction proceeded smoothly without heating or irradiation. This strategy was also expanded to the synthesis of aryl selenides.
- Bu, Mei-Jie,Lu, Guo-Ping,Cai, Chun
-
supporting information
p. 1841 - 1846
(2015/08/06)
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- Copper mediated formation of carbon-heteroatom bonds using organoboron reagents and ultrasound
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This report summarizes research efforts focused on copper acetate mediated reactions to form new carbon-heteroatom bonds using organoboron reagents under ultrasound irradiation. The method involves the application of ultrasound irradiation to the Chan-Evans-Lam reaction to achieve O-arylation of phenols, N-arylation of anilines and indoles, and S-arylation of thiols. Ultrasound irradiation was found to decrease reaction times from 72 hours to 4 hours while improving the product yields an average of 20%.1 Representative C-O, C-N, and C-S coupling reactions were successfully scaled-up from the milligram to gram levels while maintaining good product yields offering potential applications in industrial processes.
- Musolino, Bryan J.,Kabalka, George W.
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p. 271 - 297
(2015/03/04)
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- Palladium-catalyzed debenzylative cross-coupling of aryl benzyl sulfides with aryl bromides: Synthesis of diaryl sulfides
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A novel debenzylative approach to synthesize diaryl sulfides from aryl benzyl sulfides and aryl bromides in good to excellent yields is reported. Mechanistic studies suggest a single catalyst, derived from Pd(dba)2 and NiXantPhos, efficiently catalyzes α-arylation of sulfides, C-S bond cleavage, and C-S bond formation in a tricatalytic cycle. (Chemical Equation Presented).
- Mao, Jianyou,Jia, Tiezheng,Frensch, Gustavo,Walsh, Patrick J.
-
supporting information
p. 5304 - 5307
(2015/01/16)
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- Transition-metal-free acid-mediated synthesis of aryl sulfides from thiols and thioethers
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The preparation of diaryl and alkyl aryl sulfides via acid-mediated coupling of thiols and thioethers with diaryliodonium salts is reported. The scope, limitations, and mechanism of the transformation are discussed.
- Wagner, Anna M.,Sanford, Melanie S.
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p. 2263 - 2267
(2014/04/03)
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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.
-
supporting information
p. 14772 - 14779
(2015/01/16)
-
- Efficient C-N and C-S bond formation using the highly active [Ni(allyl)Cl(IPr*OMe)] precatalyst
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Two new [Ni(allyl)Cl(NHC)] complexes with the bulky yet flexible N-heterocyclic carbene (NHC) ligands IPr* {N,N'-bis[2,6- bis(diphenylmethyl)-4-methylphenyl]imidazole-2-ylidene} and IPr* OMe {N,N'-bis[2,6-bis(diphenylmethyl)-4-methoxyphenyl]imidazol-2- ylidene} are reported. These complexes were employed in the amination and sulfination of aryl halide species and were shown to perform well in these reactions, which typically required less than half as much catalyst as previous state-of-the-art nickel complexes. Copyright
- Martin, Anthony R.,Nelson, David J.,Meiries, Sebastien,Slawin, Alexandra M.Z.,Nolan, Steven P.
-
supporting information
p. 3127 - 3131
(2014/06/09)
-
- Copper oxide nanoparticles supported on graphene oxide-Catalyzed S-arylation: An efficient and ligand-free synthesis of aryl sulfides
-
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)
-
- Nickel-mediated inter- and intramolecular C-S coupling of thiols and thioacetates with aryl iodides at room temperature
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A Ni(0)-catalyzed intermolecular cross-coupling of various functionalized thiols and aryl iodides has been developed and successfully extended to less explored intramolecular versions, where thioacetates could also be utilized as the strategic surrogate. Air-stable precatalysts, very mild conditions, and an easy protocol allow rapid access to medicinally useful aryl thioethers, as demonstrated in the facile synthesis of (±)-chuangxinmycin as a key step.
- Xu, Xiao-Bo,Liu, Jian,Zhang, Jian-Jian,Wang, Ya-Wen,Peng, Yu
-
supporting information
p. 550 - 553
(2013/04/11)
-
- Room temperature Ullmann type C-O and C-S cross coupling of aryl halides with phenol/thiophenol catalyzed by CuO nanoparticles
-
C-O/C-S cross coupling of aryl halides with phenol or thiophenol was studied under ligand-free condition at room temperature over CuO nanocatalyst. The scope of the reaction was extended to various aryl halides and substituted phenols under optimized condition. In general, efficient, selective, and reusable heterogeneous nano CuO catalytic system has been developed for room temperature C-O and C-S Ullmann type cross coupling reactions.
- Babu, S. Ganesh,Karvembu
-
p. 1677 - 1680
(2013/03/28)
-
- A new family of nucleophiles for photoinduced, copper-catalyzed cross-couplings via single-electron transfer: Reactions of thiols with aryl halides under mild conditions (O C)
-
Building on the known photophysical properties of well-defined copper-carbazolide complexes, we have recently described photoinduced, copper-catalyzed N-arylations and N-alkylations of carbazoles. Until now, there have been no examples of the use of other families of heteroatom nucleophiles in such photoinduced processes. Herein, we report a versatile photoinduced, copper-catalyzed method for coupling aryl thiols with aryl halides, wherein a single set of reaction conditions, using inexpensive CuI as a precatalyst without the need for an added ligand, is effective for a wide range of coupling partners. As far as we are aware, copper-catalyzed C-S cross-couplings at 0 C have not previously been achieved, which renders our observation of efficient reaction of an unactivated aryl iodide at -40 C especially striking. Mechanistic investigations are consistent with these photoinduced C-S cross-couplings following a SET/radical pathway for C-X bond cleavage (via a Cu(I)-thiolate), which contrasts with nonphotoinduced, copper-catalyzed processes wherein a concerted mechanism is believed to occur.
- Uyeda, Christopher,Tan, Yichen,Fu, Gregory C.,Peters, Jonas C.
-
supporting information
p. 9548 - 9552
(2013/07/19)
-
- High surface and magnetically recoverable mPANI/pFe3O 4 nanocomposites for C-S bond formation in water
-
A high surface area mPANI/pFe3O4 nanocomposite from mesoporous polyaniline and porous magnetic Fe3O4 was used as a catalyst in the S-arylation of thiophenol with aryl chlorides and in the C-S bond formation between aryl iodides and thiourea in water. The mesoporosity of the polyaniline enhances the efficiency and stability of the porous magnetic Fe3O4 nanoparticles in both coupling reactions. The mPANI/pFe3O4 nanocomposite can be recovered with an external magnet and reused several times due to the superparamagnetic nature of the porous Fe3O4 nanoparticles.
- Damodara,Arundhathi,Likhar, Pravin R.
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p. 797 - 802
(2013/04/10)
-
- Chan-lam-type s-arylation of thiols with boronic acids at room temperature
-
In this work, an efficient CuSO4-catalyzed S-arylation of thiols with aryl and heteroaryl boronic acids at room temperature is established. This catalytic system can tolerate a wide variety of thiols and arylboronic acids in the presence of only 5 mol % of CuSO4 as the catalyst and inexpensive 1,10-phen?H2O as the ligand. Moreover, this catalytic system used environment-friendly solvent (EtOH) and oxidant (oxygen).
- Xu, Hua-Jian,Zhao, Yong-Qiang,Feng, Teng,Feng, Yi-Si
-
experimental part
p. 2878 - 2884
(2012/05/04)
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- Copper(I) complexes with trispyrazolylmethane ligands: Synthesis, characterization, and catalytic activity in cross-coupling reactions
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Three novel Cu(I) complexes bearing tris(pyrazolyl)methane ligands, Tpmx, have been prepared from reactions of equimolar amounts of CuI and the ligands Tpm, (HC(pz)3), Tpm, (HC(3,5-Me2-pz) 3), and TpmMs, (HC(3-Ms-pz)3). X-ray diffraction studies have shown that the Tpm and TpmMs derivatives exhibit a 2:1 Cu:ligand ratio, whereas the Tpm* complex is a mononuclear species in nature. The latter has been employed as a precatalyst in the arylation of amides and aromatic thiols with good activity. The synthesis of a TpmCu(I)-phthalimidate, a feasible intermediate in this catalytic process, has also been performed. Low temperature 1H NMR studies in CDCl 3 have indicated that this complex exists in solution as a mixture of two, neutral and ionic forms. Conductivity measurements have reinforced this proposal, the ionic form predominating in a very polar solvent such as DMSO. The reaction of TpmCu(I)-phthalimidate with iodobenzene afforded the expected C-N coupling product in 76% yield accounting for its role as an intermediate in this transformation.
- Haldon, Estela,Alvarez, Eleuterio,Nicasio, M. Carmen,Perez, Pedro J.
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experimental part
p. 8298 - 8306
(2012/09/22)
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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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- A simple, fast, and easy assay for transition metal-catalyzed coupling reactions using a paper-based colorimetric iodide sensor
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A paper-based colorimetric iodide sensor (PBCIS) that consists of filter paper treated with starch and an oxidant is developed. It has been employed as a protocol to obtain the extent of conversion of aryl iodides in C-C, C-N, C-O and C-S bond formations, including polymer-supported Heck reactions, by transition metal catalysts such as palladium, nickel and copper.
- Kim, Sudeok,Jung, Eunhye,Kim, Mi Jin,Pyo, Ayoung,Palani, Thiruvengadam,Eom, Min Sik,Han, Min Su,Lee, Sunwoo
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supporting information; scheme or table
p. 8751 - 8753
(2012/10/18)
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- Efficient recyclable CuI-nanoparticle-catalyzed S-arylation of thiols with aryl halides on water under mild conditions
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CuI nanoparticles efficiently catalyzed the C-S cross coupling of aryl and alkyl thiols with aryl halides in the absence of ligands on water under mild conditions. A wide range of diaryl sulfides and aryl alkyl sulfides are synthesized in good to excellent yields utilizing this protocol. This procedure is particularly noteworthy given its mild conditions, avoiding the undesired formation of disulfides through oxidation of thiols. The recovery and successful reutilization of the catalyst is described. Furthermore, the directed synthesis of bisarylated product is presented. The Royal Society of Chemistry 2012.
- Xu, Hua-Jian,Liang, Yu-Feng,Zhou, Xin-Feng,Feng, Yi-Si
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supporting information; experimental part
p. 2562 - 2568
(2012/04/23)
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- Efficient nickel/N-heterocyclic carbene catalyzed C-S cross-coupling
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The cross-coupling reaction of aryl halides with aliphatic and aromatic thiols catalyzed by readily available Ni(OAc)2 with N-heterocyclic carbene (NHC) is reported. Ni(OAc)2/NHC catalyst showed good activities toward various aryl halides in C-S coupling reaction, even with aryl chlorides. Reactions occurred in excellent yields, broad scope, and high tolerance of functional groups.
- Guan, Pei,Cao, Changsheng,Liu, Yun,Li, Yunfei,He, Pan,Chen, Qian,Liu, Gang,Shi, Yanhui
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supporting information
p. 5987 - 5992,6
(2012/12/12)
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- Efficient nickel/N-heterocyclic carbene catalyzed C-S cross-coupling
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The cross-coupling reaction of aryl halides with aliphatic and aromatic thiols catalyzed by readily available Ni(OAc)2 with N-heterocyclic carbene (NHC) is reported. Ni(OAc)2/NHC catalyst showed good activities toward various aryl halides in C-S coupling reaction, even with aryl chlorides. Reactions occurred in excellent yields, broad scope, and high tolerance of functional groups.
- Guan, Pei,Cao, Changsheng,Liu, Yun,Li, Yunfei,He, Pan,Chen, Qian,Liu, Gang,Shi, Yanhui
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supporting information
p. 5987 - 5992
(2013/01/13)
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- An efficient copper-catalyzed one-pot synthesis of diaryl thioethers by coupling of arylboronic acids with potassium ethyl xanthogenate under mild conditions
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A simple and environmentally benign one-pot synthesis of diaryl thioethers by coupling of arylboronic acids with potassium ethyl xanthogenate through a double arylation process has been developed. The aryl thiols were generated in situ, and the reactions proceeded smoothly to give the corresponding products in good to excellent yields under very mild conditions. Georg Thieme Verlag Stuttgart · New York.
- Wang, Liang,Zhou, Wei-You,Chen, Sheng-Chun,He, Ming-Yang,Chen, Qun
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experimental part
p. 3041 - 3045
(2012/03/11)
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- Simple and efficient copper-catalyzed S-arylation of diaryl disulfides with triarylbismuthanes under aerobic conditions
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Novel and simple copper-catalyzed C(aryl)-S bond formation of diaryl disulfides with bismuth reagents is described. Reactions of diaryl disulfides with triarylbismuthanes in the presence of CuOAc (10 mol %) and 1,10-phenanthroline (10 mol %) under aerobic conditions led to the formation of unsymmetrical diaryl sulfides in satisfactory yields. The reaction is atom-economic and all three aryl groups of the triarylbismuthanes and both sulfanyl groups of the diaryl disulfides could be transferred to the coupling products.
- Yasuike, Shuji,Nishioka, Motokazu,Kakusawa, Naoki,Kurita, Jyoji
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experimental part
p. 6403 - 6406
(2011/12/22)
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- A ligand-free copper-catalyzed decarboxylative trifluoromethylation of aryliodides with sodium trifluoroacetate using Ag2O as a promoter
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A practical and ligand-free Cu-catalyzed decarboxylative trifluoromethylation of aryl iodides with sodium trifluoroacetate using Ag 2O as a promoter was reported. A variety of trifluoromethyl- substituted aromatics are synthesized in moderate to excellent yields and with wide functional-group tolerance under relatively mild reaction conditions. Georg Thieme Verlag Stuttgart · New York.
- Li, Yaming,Chen, Tao,Wang, Huifeng,Zhang, Rong,Jin, Kun,Wang, Xiuna,Duan, Chunying
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supporting information; experimental part
p. 1713 - 1716
(2011/09/12)
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- Diazaphospholane as an efficient ligand for copper-catalyzed cross-coupling of thiols with aryl iodides
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Copper-catalyzed cross-coupling of thiols with aryl iodides performed well using an air-stable diazaphospholane ligand in presence of NaOH in DMF at 110 °C and a variety of diaryl sulfides are synthesized in good yields.
- Yang, Minghua,Pei, Ji,Yan, Guobing,Zheng, Yunfa
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experimental part
p. 587 - 591
(2012/05/31)
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- Efficient copper(I)-catalyzed C-S cross-coupling of thiols with aryl halides in an aqueous two-phase system
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A mild and convenient C-S bond formation reaction catalyzed by CuI/L-proline in an aqueous two-phase system was achieved, providing a simple method for the synthesis of aryl sulfides in good yields.
- Zhang, Xin-Yan,Zhang, Xiao-Yan,Guo, Sheng-Rong
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experimental part
p. 23 - 35
(2011/12/05)
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- One-pot synthesis of unsymmetrical diaryl thioethers by palladium-catalyzed coupling of two aryl bromides and a thiol surrogate
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Extraordinarily simple, convenient, and efficient: A general and operationally simple one-pot synthesis of unsymmetrical diaryl sulfides by coupling two different bromoarenes and triisopropylsilanethiol (TIPS-SH) is reported. This protocol overcomes the narrow availability of arene thiols and their instability to oxidation. These reactions catalyzed by palladium complexes generated from the alkylbisphosphine CyPF-tBu occur in good to excellent yields with wide scope and high tolerance of functional groups.
- Fernandez-Rodriguez, Manuel A.,Hartwig, John F.
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supporting information; experimental part
p. 2355 - 2359
(2010/07/02)
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- Mechanistic insights into C-S cross-coupling reactions catalyzed by nickel bis(phosphinite) pincer complexes
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Nickel bis(phosphinite) pincer complexes [2,6-(R2PO) 2C6H3]NiCl (R = Ph, 1a; R = Me, 1b; R = iPr, 1c; R = tBu, 1d) show catalytic activity in cross-coupling of aryl iodides and aryl thiols. The optimal catalytic conditions involve 1 mol % of 1a and 2 equiv of KOH (with respect to aryl thiols) in DMF at 80 °C and tolerate a variety of functional groups in the substrates. The potential intermediates in these catalytic reactions, such as nickel thiolate complexes [2,6-(Ph2PO)2C6H3]NiSAr (Ar = Ph, 2a; Ar = p-MeC6H4, 3a; Ar = p-MeOC 6H4, 4a), have been synthesized and spectroscopically characterized. The reaction between 2a and PhI in DMF-d7 is slow enough to argue against 2a being directly involved in the C-S bond-forming step. NMR studies suggest that the pincer ligand framework in complexes 1a, 3a, and 4a is destroyed by KOH via the cleavage of P-O bonds to release Ph 2POK, and further decomposition leads to Ph3P and other phosphorus-containing products. The cross-coupling reactions are more effectively catalyzed by Ni(COD)2/Ph2P(O)H. The structures of 1b, 2a, 4a, and [2,6-(Ph2PO)2C6H 3]NiP(O)Ph2 (5a), which is relevant to the decomposition process, have been studied by X-ray crystallography.
- Zhang, Jie,Medley, Christopher M.,Krause, Jeanette A.,Guan, Hairong
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experimental part
p. 6393 - 6401
(2011/02/17)
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- Efficient copper-catalyzed S-arylation of thiols with aryl bromides and chlorides
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An efficient copper-catalyzed system for C-S cross-coupling of aromatic thiols with aryl bromides and chlorides has been developed using 1,2,3,4-tetrahydroquinoline-8-ol as a ligand. It is noteworthy that this method is proved to be especially effective for aryl bromides with electron-donating groups. By this protocol, a variety of thioethers as well as symmetrical and unsymmetrical bis-thioethers are obtained in excellent yields with an exceptional level of functional group tolerance and high chemoselectivity. Georg Thieme Verlag Stuttgart - New York.
- Li, Yaming,Li, Xiaoying,Wang, Huifeng,Chen, Tao,Xie, Yusheng
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supporting information; experimental part
p. 3602 - 3608
(2010/12/19)
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- Efficient C-S cross coupling catalyzed by Cu2O
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A protocol for the copper-catalyzed C-S bond formation between aryl, alkyl, or heteroaryl thiols and aryl or heteroaryl halides is reported. The reaction is catalyzed by Cu2O which shows the highest catalytic activity with ethyl 2-oxocyclohexanecarboxylate ligand in DMSO at 80 °C. The corresponding coupling products are obtained with good to excellent yields under relatively mild reaction conditions with good chemoselectivity and functional group tolerance.
- Xu, Hua-Jian,Zhao, Xiao-Yang,Deng, Jin,Fu, Yao,Feng, Yi-Si
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experimental part
p. 434 - 437
(2009/05/11)
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