- Transition-Metal-Free HFIP-Mediated Organo Chalcogenylation of Arenes/Indoles with Thio-/Selenocyanates
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We have developed a protocol for the synthesis of diaryl thio-/selenoethers by the reaction of aryl chalcogenocyanates with electron rich arenes/hetero arenes via HFIP promoted C-H activation. The reaction produces chalcogenides in good to excellent yields under mild conditions without the need of a transition metal as a catalyst. The HFIP-mediated reactions tolerated a wide range of functional groups and set the stage for the synthesis of diversely decorated chalcogenides. A mechanism involving activation of the C-H bond through hydrogen bonding is proposed.
- Goswami, Avijit,Kalaramna, Pratibha
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supporting information
p. 9317 - 9327
(2021/07/26)
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- Direct C-H Thiolation for Selective Cross-Coupling of Arenes with Thiophenols via Aerobic Visible-Light Catalysis
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An aerobic metal-free, visible-light-induced regioselective thiolation of phenols with thiophenols is reported. The cross-coupling protocol exhibits great functional group tolerance and high regioselectivity. Mechanistic studies reveal that the disulfide
- Chen, Bin,Chen, Ya-Jing,Cheng, Yuan-Yuan,Lei, Tao,Liang, Ge,Tung, Chen-Ho,Wang, Jing-Hao,Wu, Li-Zhu,Ye, Chen,Zhou, Chao
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supporting information
p. 8082 - 8087
(2021/10/25)
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- Metal-and oxidant-free electrochemical synthesis of aryl sulfides
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A metal- and oxidant-free electrochemical synthesis of aryl sulfides was developed through a C–H sulfidation reaction of arenes and disulfides. Compared with traditional organic synthesis methods, this direct electrochemical approach efficiently generates aryl sulfides under catalyst- and oxidant-free conditions with the superiorities of wide substrate compatibility, mild reaction condition and waster free. At room temperature, various aryl thiols could be transformed smoothly in an undivided cell. Based on cyclic voltammetry (CV) and control experiments, the possible reaction mechanism was also proposed. The gram-scale synthesis emphasizes the practicability of this electrochemical strategy.
- Wang, Xin-Xing,Chen, Cheng,Shi, Hai-Zhu,Zhang, Guo-Wei,Tang, Yu,Zhang, Chun-Gu,Wu, Ming-Yu,Feng, Shun
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- Scalable electrochemical reduction of sulfoxides to sulfides
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A scalable reduction of sulfoxides to sulfides in a sustainable way remains an unmet challenge. This report discloses an electrochemical reduction of sulfoxides on a large scale (>10 g) under mild reaction conditions. Sulfoxides are activated using a substoichiometric amount of the Lewis acid AlCl3, which could be regeneratedviaa combination of inexpensive aluminum anode with chloride anion. This deoxygenation process features a broad substrate scope, including acid-labile substrates and drug molecules.
- Kong, Zhenshuo,Pan, Chao,Li, Ming,Wen, Lirong,Guo, Weisi
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supporting information
p. 2773 - 2777
(2021/04/21)
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- Electrochemical access to aryl sulfides from aryl thiols and electron-rich arenes with the potassium iodide as a mediator
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An indirect electrooxidation method catalyzed by potassium iodide at a low potential for the synthesis of aryl sulfides from aryl thiols and electron-rich arenes has been developed. Cyclic voltammetry was carried out to investigate the electrocatalytic ac
- Liu, Xin,Niu, Pengfei,Jin, Jiali,Shen, Zhenlu,Li, Meichao
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- Aerobic Oxidative Sulfenylation of Pyrazolones and Pyrazoles Catalyzed by Metal-Free Flavin-Iodine Catalysis
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Two-component metal-free catalytic oxidative sulfenylation of pyrazolones with thiols has been achieved using the biomimetic flavin and iodine. The methodology is mild and eco-friendly, proceeds in the presence of air or molecular oxygen (1 atm) as the sole sacrificial reagent, and generates water as the only byproduct. The methodology was also extended to the sulfenylation of pyrazoles and electron-rich benzenes and afforded a series of thioethers in good yields.
- Tanimoto, Kazumasa,Ohkado, Ryoma,Iida, Hiroki
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supporting information
p. 14980 - 14986
(2019/11/13)
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- Palladium(II)/Copper(II)-Catalyzed C–H Sulfidation or Selenation of Arenes Leading to Unsymmetrical Sulfides and Selenides
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A novel palladium(II)/copper(II)-catalyzed sulfidation of the C–H bond in electron-rich arenes and in pentafluorobenzene with disulfides was developed. This catalytic system can be used to efficiently produce various types of either unsymmetrical aryl sulfides or alkyl aryl sulfides. The present protocol could also be applied to the direct preparation of unsymmetrical aryl selenides via C–H selenation.
- Nishino, Kota,Tsukahara, Shouya,Ogiwara, Yohei,Sakai, Norio
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supporting information
p. 1588 - 1593
(2019/02/09)
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- Phenyliodine(III) Bis(trifluoroacetate) (PIFA)-Mediated Synthesis of Aryl Sulfides in Water
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An environmentally benign method for the synthesis of aryl sulfides in water under mild conditions has been realized, in which arenes are coupled with equal stoichiometry of allyl sulfides. This arylthiolation is enabled by the presence of the Lipshutz su
- Feng, Qingyuan,Chen, Dengfeng,Hong, Mei,Wang, Fei,Huang, Shenlin
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p. 7553 - 7558
(2018/05/14)
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- Cobalt-Catalyzed Aerobic Cross-Dehydrogenative Coupling of C-H and Thiols in Water for C-S Formation
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Organosulfides have great significance and value in synthetic and biological chemistry. To establish a versatile and green methodology for C-S bond generation, we successfully developed a new aerobic cross-dehydrogenative coupling of C-H and S-H to synthe
- Huang, Xin,Chen, Yongqi,Zhen, Shan,Song, Lijuan,Gao, Mingqi,Zhang, Panke,Li, Heng,Yuan, Bingxin,Yang, Guanyu
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p. 7331 - 7340
(2018/07/29)
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- Cu-catalyzed direct C-H thiolation of electron-rich arenes with arylsulfonyl hydrazides
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An efficient Cu-catalyzed direct C–H thiolation of electron-rich arenes with arylsulfonyl hydrazides has been developed. Various mono(or bis)-thioether products were obtained in moderate to good yields. Mechanistic studies suggest that the reaction likely proceeds through free-radical formation including arylthio radical and sulfonyl radical, while both disulfanes and sulfonothioates are the major thiolation species in this transformation.
- Chen, Lingjuan,Liu, Ping,Wu, Jianglong,Dai, Bin
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p. 1513 - 1519
(2018/02/21)
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- Sodium Iodide (NaI)-Catalyzed Cross-Coupling for C?S Bond Formation via Oxidative Dehydrogenation: Cheap, Direct Access to Unsymmetrical Aryl Sulfides
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A simple and practical NaI-catalyzed direct C?H sulfenylation of arenes has been developed under air. In this reaction, aryl sulfides were obtained in moderate to excellent yields with high regioselectivity from readily available aromatic compounds and aryl/alkyl thiols, even on gram scale. To demonstrate the practicability of this reaction, two bioactive compound skeletons were synthesized in good yields. This method can also be used to late-stage modification of curcumin.
- Wang, Hui-Hong,Shi, Tao,Gao, Wei-Wei,Wang, Yong-Qiang,Li, Jun-Fang,Jiang, Yi,Hou, Yong Sheng,Chen, Chen,Peng, Xue,Wang, Zhen
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supporting information
p. 2675 - 2679
(2017/10/18)
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- Thieme Chemistry Journals Awardees - Where Are They Now?Molybdenum(V)-Mediated Synthesis of Nonsymmetric Diaryl and Aryl Alkyl Chalcogenides
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Oxidative chalcogenation reaction using molybdenum(V) reagents provides fast access to a wide range of nonsymmetric aryl sulfides and selenides. The established protocol is tolerated by a variety of labile functions, protecting groups, and aromatic heterocycles. In particular, when labile moieties are present, the use of molybdenum(V) reagents provides superior yields compared to other oxidants.
- Franzmann, Peter,Beil, Sebastian B.,Winterscheid, Peter M.,Schollmeyer, Dieter,Waldvogel, Siegfried R.
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supporting information
p. 957 - 961
(2017/05/05)
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- Iodine-catalyzed thiolation of electron-rich aromatics using sulfonyl hydrazides as sulfenylation reagents
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Iodine-catalyzed thiolation of electron-rich aromatics, including substituted anisole, thioanisole, phenol, toluene, and naphthalene, using sulfonyl hydrazides as sulfenylation reagents was carried out. Sulfonothioates, the products of decomposition of sulfonyl hydrazides in the presence of iodine, are proposed as the major sulfenylation species in this transformation.
- Zhao, Xia,Li, Tianjiao,Zhang, Lipeng,Lu, Kui
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p. 1131 - 1137
(2016/01/15)
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- N-Chlorosuccinimide promoted direct C(sp2)–H bond thiolation of the methoxybenzenes with thiophenols
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A simple and an efficient procedure for the formation of diaryl sulfides via direct sp2C–H functionalization have been developed from simple and readily available thiophenols and substituted methoxy benzenes. In this process thiophenols were us
- Raghavender Reddy,Kumar, G. Santosh,Meshram
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supporting information
p. 3622 - 3624
(2016/07/22)
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- Radical-Radical Cross-Coupling for C-S Bond Formation
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A new method was demonstrated to overcome the selectivity issue of radical-radical cross-coupling toward the synthesis of asymmetric diaryl thioethers. The preliminary mechanism was revealed by radical-trapping experiments, DFT calculations, and kinetics,
- Huang, Zhiliang,Zhang, Dongchao,Qi, Xiaotian,Yan, Zhiyuan,Wang, Mengfan,Yan, Haiming,Lei, Aiwen
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supporting information
p. 2351 - 2354
(2016/06/09)
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- TBAI-HBr system mediated generation of various thioethers with benzenesulfonyl chlorides in PEG400
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An efficient procedure for the formation of C-S bonds via C-H functionalization was developed for the synthesis of aryl sulfides in good to excellent yields using TBAI-HBr system promoted direct sulfenylation of various compounds, such as phenols, pyrazolones, indoles and related heteroarenes. Low cost and widely available arylsulfonyl chlorides were used as the sulfur source to provide various sulfur-containing compounds. The characteristic of the present protocol is convenient, green, highly efficient with a wide-application and short reaction time.
- Wang, Dingyi,Guo, Shengmei,Zhang, Rongxing,Lin, Sen,Yan, Zhaohua
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p. 54377 - 54381
(2016/07/06)
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- Iodine catalyzed cross-dehydrogenative C-S coupling by C(sp2)-H bond activation: Direct access to aryl sulfides from aryl thiols
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A novel, efficient and unprecedented green protocol for the formation of C-S bonds has been developed under metal-free conditions. This protocol involves the synthesis of aryl sulfides through the cross-dehydrogenative coupling of readily available aryl t
- Parumala, Santosh Kumar Reddy,Peddinti, Rama Krishna
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supporting information
p. 4068 - 4072
(2015/07/15)
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- Direct thiolation of methoxybenzenes with thiols under metal-free conditions by iodine catalysis
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A direct thiolation of methoxybenzenes with various thiols has been developed. The protocol uses inexpensive reagents: catalytic iodine in the presence of DTBP. Importantly, no base or ligand was necessary. This method opens a new avenue to a variety of valuable thioethers that would be more difficult to access with traditional methods.
- Yan, Kelu,Yang, Daoshan,Sun, Pengfei,Wei, Wei,Liu, Yao,Li, Guoqing,Lu, Shenglei,Wang, Hua
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supporting information
p. 4792 - 4795
(2015/07/20)
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- Synthesis of Aryl Sulfides: Metal-Free C-H Sulfenylation of Electron-Rich Arenes
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A simple, efficient, and practical metal-free C-H sulfenylation of substituted electron-rich arenes has been developed. This method is highly regioselective, and the corresponding aryl sulfides were obtained in moderate to excellent yields from stable and
- Hostier, Thomas,Ferey, Vincent,Ricci, Gino,Gomez Pardo, Domingo,Cossy, Janine
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p. 3898 - 3901
(2015/08/18)
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- Copper-catalyzed aerobic oxidative N-S bond functionalization for C-S bond formation: Regio- and stereoselective synthesis of sulfones and thioethers
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A regio- and stereoselective synthesis of sulfones and thioethers by means of CuI-catalyzed aerobic oxidative N-S bond cleavage of sulfonyl hydrazides, followed by cross-coupling reactions with alkenes and aromatic compounds to form the C-sp-2-S bond, is described herein. N2 and H2O are the byproducts of this transformation, thus offering an environmentally benign process with a wide range of potential applications in organic synthesis and medicinal chemistry. First cleave, then cross-couple: A direct Cu-catalyzed aerobic oxidative C-sp-2-H functionalization and C-S bond coupling reaction has been developed (see scheme). By slight modification of the additive, sulfonyl hydrazides could serve as sulfonation, sulfenation, or arylation reagents to undergo cross-coupling reactions with alkenes and (hetero)aromatic cycles, affording sulfones, thioethers, and biaryl compounds with high regio- and stereoselectivities (see scheme).
- Li, Xianwei,Xu, Yanli,Wu, Wanqing,Jiang, Chang,Qi, Chaorong,Jiang, Huanfeng
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supporting information
p. 7911 - 7915
(2014/07/07)
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- Iron-catalyzed direct C-H thiolation of trimethoxybenzene with disulfides
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(Chemical Equation Presented) An iron-catalyzed thiolation access to sulfides from disulfides via arene C-H bond cleavage of trimethoxybenzene is described. The procedure tolerates methoxyl, fluoro, chloro, bromo, nitro, and heterocyclic groups, using air
- Zhang, Manli,Zhang, Shouhui,Pan, Changduo,Chen, Fan
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experimental part
p. 2844 - 2853
(2012/08/14)
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- Synthesis of di(hetero)aryl sulfides by directly using arylsulfonyl chlorides as a sulfur source
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A new, efficient protocol for the synthesis of di(hetero)aryl sulfides is described. Cheap and easily available arylsulfonyl chlorides as a sulfur source reductively couple with electron-rich (hetero)arenes (e.g., indolizines, indoles, electron-rich benzenes, etc.) in the presence of triphenylphosphine to afford di(hetero)aryl thioethers in good yields.
- Wu, Qian,Zhao, Dongbing,Qin, Xurong,Lan, Jingbo,You, Jingsong
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supporting information; experimental part
p. 9188 - 9190
(2011/10/04)
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- Novel C-H functionalization of arenes: Palladium-catalyzed synthesis of diaryl sulfides
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A novel protocol for the direct arylthiolation of electron-rich arenes is described. Applying arylsulfonyl cyanides in the presence of catalytic amounts of Pd allows for a straightforward synthesis of diaryl sulfides.
- Anbarasan, Pazhamalai,Neumann, Helfried,Beller, Matthias
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supporting information; experimental part
p. 3233 - 3235
(2011/05/05)
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- Copper-catalyzed thiolation of the Di- or trimethoxybenzene arene C-H bond with disulfides
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A CuI-catalyzed direct access to sulfides from disulfides via C-H bond cleavage of di- or trimethoxybenzene is described. The procedure utilizes O 2 as a clean and cheap oxidant. Direct selenation of the C-H bond also took place under this procedure. Furthermore, the system enables the use of two RS in (RS)2. Thus, it represents an atom-economical procedure for the synthesis of sulfides and selenides.
- Zhang, Shouhui,Qian, Pengcheng,Zhang, Manli,Hu, Maolin,Cheng, Jiang
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experimental part
p. 6732 - 6735
(2010/12/19)
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