- 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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- 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
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supporting information
p. 6164 - 6168
(2021/08/16)
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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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- 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
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supporting information
p. 2326 - 2331
(2020/05/05)
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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
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supporting information
p. 10087 - 10091
(2017/08/01)
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- Nickel-Schiff base complex catalyzed C-S cross-coupling of thiols with organic chlorides
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We report an efficient, mild and convenient synthetic protocol for the C-S cross-coupling reaction of various aryl, benzyl, allyl chlorides and thiols using 5 mol % Nickel-Schiff base catalyst with NaOH as the base, in DMF at 70 °C. Using this protocol, we have shown that a variety of aryl sulfides can be synthesized in excellent yields from readily available organic chlorides and thiols.
- Gogoi, Prasanta,Hazarika, Sukanya,Sarma, Manas J.,Sarma, Kuladip,Barman, Pranjit
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p. 7484 - 7489
(2014/12/10)
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- An efficient protocol for the carbon-sulfur cross-coupling of sulfenyl chlorides with arylboronic acids using a palladium catalyst
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An efficient protocol for carbon-sulfur bond formation is developed, which involves the cross-coupling of sulfenyl chlorides and arylboronic acids catalyzed by a novel palladium-Schiff base complex. Good to high product yields, short reaction times, and mild reaction conditions are important features of this new method. Georg Thieme Verlag Stuttgart · New York.
- Gogoi, Prasanta,Kalita, Mukul,Barman, Pranjit
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p. 866 - 870
(2014/04/03)
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- Efficient C-S cross-coupling of thiols with aryl iodides catalyzed by Cu(OAc)2·H2O and 2,2′-biimidazole
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The classical Ullmann C-S cross coupling reaction of aryl iodides with aromatic/alkyl thiols under catalysis of 15 mol% Cu(OAc)2· H2O and 15 mol% 2,2′-biimidazole works at 80°C in DMSO for 3 h to provide a variety of aryl sulfides in good to excellent yields. The classical Ullmann C-S cross coupling reaction of aryl iodides with aromatic/alkyl thiols under catalysis of 15 mol% Cu(OAc)2· H2O and 15 mol% 2,2′-biimidazole works at 80°C in DMSO for 3 h to provide a variety of aryl sulfides in good to excellent yields. Copyright
- Zong, Chenglong,Liu, Jianli,Chen, Shengyan,Zeng, Runsheng,Zou, Jianping
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supporting information
p. 212 - 218
(2014/04/03)
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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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- Chan-lam-type s-arylation of thiols with boronic acids at room temperature
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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
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experimental part
p. 2878 - 2884
(2012/05/04)
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- 8-hydroxyquinolin-N-oxide-promoted copper-catalyzed C-S cross-coupling of thiols with aryl iodides
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8-Hydroxyquinolin-N-oxide was identified as a superior ligand for CuI-catalyzed C-S coupling reactions of aryl iodides with thiols to afford the corresponding thioethers in excellent yield. The method shows excellent chemoselectivity and high functional-group tolerance in both coupling partners. Copyright
- Su, Kun,Qiu, Yatao,Yao, Yiwu,Zhang, Dayong,Jiang, Sheng
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supporting information
p. 2853 - 2857
(2013/02/21)
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- Cross-coupling reactions of aryl halides with amines, phenols, and thiols catalyzed by an N,N′-dioxide-copper(I) catalytic system
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The coupling reactions of various N, O, and S nucleophilic reagents with aryl halides have been successfully carried out under mild conditions by using a novel chiral N,N′-dioxide-copper(I) catalytic system as the catalyst. This versatile and efficient catalyst system has been demonstrated to facilitate the cross-coupling reactions of aryl halides with amines, phenols, and thiols to afford the corresponding desired products in good to excellent yields.
- Yang, Haitao,Xi, Chao,Miao, Zhiwei,Chen, Ruyu
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supporting information; experimental part
p. 3353 - 3360
(2011/08/03)
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- The synthesis and SAR of novel diarylsulfone 11β-HSD1 inhibitors
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In this communication, human 11β-hydroxysteroid dehydrogenase type 1 (11β-HSD1) inhibitory activities of a novel series of diarylsulfones are described. Optimization of this series resulted in several highly potent 11β-HSD1 inhibitors with excellent pharmacokinetic (PK) properties. Compound (S)-25 showed excellent efficacy in a non-human primate ex vivo pharmacodynamic model.
- Yan, Xuelei,Wang, Zhulun,Sudom, Athena,Cardozo, Mario,Degraffenreid, Michael,Di, Yongmei,Fan, Pingchen,He, Xiao,Jaen, Juan C.,Labelle, Marc,Liu, Jinsong,Ma, Ji,McMinn, Dustin,Miao, Shichang,Sun, Daqing,Tang, Liang,Tu, Hua,Ursu, Stefania,Walker, Nigel,Ye, Qiuping,Powers, Jay P.
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scheme or table
p. 7071 - 7075
(2011/01/03)
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- Deoxygenation of sulfoxides, selenoxides, telluroxides, sulfones, selenones and tellurones with Mg-MeOH
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The deoxygenation of a variety of sulfoxides, selenoxides, telluroxides, sulfones, selenones and tellurones has been reported with Mg-MeOH at room temperature in nearly quantitative yields. The deoxygenation is proposed to proceed by SET from Mg to the substrate.
- Khurana, Jitender M.,Sharma, Vandana,Chacko, Silvi A.
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p. 966 - 969
(2007/10/03)
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- One-step arylthiolation of aromatic compounds by disulfide radical cations generated from oxidation of diaryl disulfides with aluminium chloride
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Reactions of di(phenyl and 4-tolyl) disulfides 1a and 1b with PhX 3a-e (X = H, Me, Et, Ph and Cl) in the presence of AlCl3 at 25°C give diaryl sulfides 4-6 by aromatic arylthiolation via the disulfide radical cations 2, along with thiophenols 7 formed in the incomplete reactions. Competitive intramolecular reactions of 2a also yield diphenyl sulfide 4a or/and thianthrene 8. However, the reactions of bis(4-chlorophenyl and 4-fluorophenyl) disulfides 1c and 1d selectively lead to the aromatic arylthiolation in high yields. The Hammett ρ = -8.8 at 25°C for the phenylthiolation in the reactions of 1a is more negative than that (ρ = -7.0 at -30°C) using SbCl5 instead of AlCl3, and the value ρ = -8.0 for the arylthiolation using 1d is less negative than that using 1a. These and the other mechanistic aspects support the arylthiolations via 2.
- Takeuchi, Hiroshi,Suga, Keisuke
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p. 1803 - 1808
(2007/10/03)
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- Alkyl- and Arylthiodediazoniations of Dry Arenediazonium o-Benzenedisulfonimides. Efficient and Safe Modifications of the Stadler and Ziegler Reactions to Prepare Alkyl Aryl and Diaryl Sulfides
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The reaction between dry arenediazonium o-benzenedisulfonimides 1 and sodium thiolates in anhydrous methanol represents an efficient and safe procedure, of general validity, for the preparation of unfunctionalized or variously functionalized alkyl aryl and diaryl sulfides. As a rule, the reaction temperature was maintained at 0-5°C for the alkylthiodediazoniations and at room temperature (20-25°C) for the arylthiodediazoniations. The sulfide yields are generally high; of the 63 considered examples, 43 gave yields greater than 80% and 13 were between 70% and 80%. Lower yields were obtained only when sterically hindered diazonium salts or thiols were used. A good amount of the o-benzenedisulfonimide (8) was always recovered from the reactions and could be reused to prepare salts 1. The copious experimental data collected in homogeneous conditions have offered several starting points for the study of the mechanism of these reactions.
- Barbero, Margherita,Degani, Iacopo,Diulgheroff, Nicola,Dughera, Stefano,Fochi, Rita,Migliaccio, Mara
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p. 5600 - 5608
(2007/10/03)
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- Directed Metalation of Benzenesulfinamides. A Novel Route to Meta-Substituted Aromatic Compounds
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Directed lithiation ortho to the sulfinamide group of readily available ortho- and para-substituted N-phenylbenzenesulfinamides (5a-d) and reaction with a variety of electrophiles followed by mercuridesulfination (HgCl2) or dehydrodesulfination (Ra/Ni) co
- Katritzky, Alan R.,Lue, Ping
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- Monosubstitution versus Disubstitution in the SRN1 Reaction of Dihalobenzenes with Sulfanions. The Role of the Monosubstitution Product and of Its Anion Radical
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The competition between mono- and disubstitution of dihalobenzenes by a series of aromatic sulfanions, via the SRN1 reaction, is shown to involve two radical chains.The first one, recognized in earliest works, involves one branching point at the level of the monosubstituted product anion radical.Reoxidation of the latter via electron transfer to the parent dihalide affords the monosubstituted product.Conversely, the route to the disubstituted product is opened when cleavage of the carbon-halogen bond in the monosubstituted product anion radical occurs before the electron transfer takes place; the disubstitution product is then obtained in its reduced (anion radical) form.Reoxidation of the latter, to afford the neutral disubstituted product, may involve competitively the parent dihalide or the neutral monosubstituted product, depending on the electron affinity of the arylthio moiety.In the first case the electron transfer propagates the first chain; in the second a new chain leading to the disubstitution is activated.The role of the two imbricated chains, under photochemical conditions, and thus that of the monosubstitution product is discussed quantitatively on the basis of the pertinent rate constants determined by cyclic voltammetry.
- Amatore, C.,Beugelmans, R.,Bois-Choussy, M.,Combellas, C.,Thiebault, A.
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p. 5688 - 5695
(2007/10/02)
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- A MILD AND EFFICIENT SRN1 APPROACH TO DIARYL SULFIDES FROM ARENEDIAZONIUM TETRAFLUOROBORATES
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The reaction between arenediazonium tetrafluoroborates and sodium arenethiolates in Me2SO at 25 deg C represent an efficient access to diaryl sulfides.A number of evidences suggest the occurance of a radical, radical-anion SRN1 mechanism, the arenethiolate acting both as electron donor and as aryl-radical trapping nucleophile.Valuable improvements with respect to recent SRN1 syntheses of diaryl sulfides from haloarenes are represented, inter alia, by the compatibility of both electron-withdrawing and relasing substituents as well as by the intensivity to steric hindrance in the diazonium salt.When the arenediazonium ion bears another SRN1 leaving group (such as Cl, Br, or I) disubstitution products are predominantly formed.
- Petrillo, Giovanni,Novi, Marino,Garbarino, Giacomo,Dell'Erba, Carlo
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p. 4007 - 4016
(2007/10/02)
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