- Chalcogenylation of Naphthalene Derivatives Catalyzed by Iron(III) Chloride and Potassium Iodide
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We have developed an efficient chalcogenylation of electron-rich naphthalene derivatives catalyzed by FeCl 3and KI. The methodology provides access to several nonsymmetrical diorganoyl chalcogenides (S, Se) by selective C1 chalcogenylation of 2
- Seckler, Diego,Da Luz, Eduardo Q. Da,Silvério, Gabriel L.,Badshah, Gul,Lima, David B.,Abreu, Emerson A.,Albach, Breidi,Ribeiro, Ronny R.,Rampon, Daniel S.
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supporting information
p. 940 - 946
(2021/04/15)
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- Aerobic Cross-Dehydrogenative Coupling Reactions for Selective Mono- And Dithiolation of Phenols
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A highly efficient strategy for the direct thiolation of phenols under transition metal-free and solvent-free conditions has been developed. These reactions are operationally simple with employing air (molecular oxygen) as an ideal oxidant and can selectively provide mono- and dithiolation products in good to excellent yields under basic conditions. The reaction tolerates a broad range of aryl thiols and arenes and is especially applicable for large-scale synthesis.
- Han, Dong-Yang,Liu, Xiao-Peng,Li, Ruo-Pu,Xu, Da-Zhen
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p. 10166 - 10176
(2021/07/31)
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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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- Regioselective Ortho‐C–H sulfenylation of free phenols catalyzed by Co(II)-immobilized on silica-coated magnetic nanoparticles
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Fe3O4?SiO2-UT?CoII is prepared by the silica-coated magnetic nanoparticles, urea-triazole, and CoCl2. This organic-inorganic hybride composite showed a good to excellent catalytic activity toward regioselective ortho-sulfenylation of free phenols and naphthols using pivalic anhydride as a directing group, also K2S2O8 and PPh3 were employed as oxidant and additive respectively. The newly synthesized catalyst was fully characterized by using different techniques such as FT-IR, TGA, DTG, TEM, SEM, EDS, ICP and VSM analyses. The competitive price, accessibility and lower toxicity of cobalt compared to expensive transition metals using for C–H bond activation and functionalization constitute precious advantages for this method. Moreover, this heterogeneous catalyst could be magnetically recovered and reused without significant loss of its catalytic activity after five cycles.
- Khaef, Sepideh,Rostami, Abed,Khakyzadeh, Vahid,Zolfigol, Mohammad Ali,Taherpour, Avat Arman,Yarie, Meysam
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- Metal- And solvent-free direct C-H thiolation of aromatic compounds with sulfonyl chlorides
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A simple, efficient and green method for the direct thiolation of aromatic compounds using commercially available sulfonyl chlorides as the sulfur source was developed under metal- and solvent-free conditions. The C-S bond was constructed via direct C-H functionalization of diverse aromatic compounds under an oxygen atmosphere. In this process, various diaryl sulfides were synthesized in moderate to excellent yields. This protocol shows a broad substrate scope and good functional group tolerance. Moreover, a gram-scale experiment was also conducted to prove the prospect of this method for the scale-up synthesis of diaryl sulfides. Mechanistic studies indicate that this procedure probably undergoes a radical pathway.
- Zhao, Feng,Tan, Qi,Wang, Dahan,Deng, Guo-Jun
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supporting information
p. 427 - 432
(2020/02/13)
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- CuI-catalyzed direct synthesis of diaryl thioethers from aryl boronic acids and arylsulfonyl chlorides
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A CuI-catalyzed direct coupling of aryl boronic acids with arylsulfonyl chlorides for the preparation of diaryl thioethers was developed. The reaction is initiated by a PPh3 reduction of the arylsulfonyl chloride, followed by a CuI-catalyzed C–S coupling with an aryl boronic acid. Various arylsulfonyl chlorides can directly serve as a sulfur source in this mild and efficient reaction giving the desired products in moderate to good yields. Moreover, this practical method has also been applied to the thioetherification of aryl iodides and acetylacetones.
- Huang, Keke,Yang, Min,Lai, Xiao-Jing,Hu, Xin,Qiu, Guanyinsheng,Liu, Jin-Biao
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- TBAI-mediated sulfenylation of arenes with arylsulfonyl hydrazides in DPDME
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An efficient TBAI (tetrabutylammonium iodide)-mediated C–H sulfenylation of arenes with arylsulfonyl hydrazides in dipropylene glycol dimethyl ether (DPDME) was described. Various electron-rich arenes were applicable in the reaction, such as naphthylamine, naphthol, aniline, indole, pyrrole, and imidaz o [1,2-a] pyridine. A wide range of the aryl sulfides were obtained with good functional group tolerance. This method features green reaction conditions (odorless and easily available sulfur reagent, recyclable TBAI, and DPDME as solvent), and broad substrate scope. The synthetic potential is demonstrated by gram-scale synthesis and downstream transformations. The mechanism studies show that the reaction is achieved through electrophilic substitution process, and diaryl disulfide may be the main intermediate.
- Jie, Zhang,Jing, He,Ping, Liu,Xuezhen, Li,Yali, Liu,Yueting, Wei
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supporting information
(2020/10/13)
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- Synergistic Dual Role of [hmim]Br-ArSO2Cl in Cascade Sulfenylation-Halogenation of Indole: Mechanistic Insight into Regioselective C-S and C-S/C-X (X = Cl and Br) Bond Formation in One Pot
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Bifunctionalized indoles are an important class of biologically active heterocyclic compounds and potential drug candidates. Because of the lack of efficient synthetic methods, one pot cascade synthesis of these compounds is rare and remains a challenge.
- Equbal, Danish,Singh, Richa,Saima,Lavekar, Aditya G.,Sinha, Arun K.
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p. 2660 - 2675
(2019/03/14)
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- Metal free, facile sulfenylation of ketene dithioacetals catalyzed by an HBr-DMSO system
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A transition metal free, highly efficient, sulfenylation of ketene dithioacetals catalyzed by an HBr-DMSO system is achieved. This strategy employs inexpensive and readily available HBr and DMSO to provide a direct C-H bond sulfenylation with a broad rang
- Sorabad, Ganesh Shivayogappa,Maddani, Mahagundappa Rachappa
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supporting information
p. 5996 - 6000
(2019/04/16)
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- Lewis Base/Bronsted Acid Dual-Catalytic C-H Sulfenylation of Aromatics
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A Lewis base/Bronsted acid catalyzed aromatic sulfenylation is reported. These studies demonstrated that the incorporation of electron-rich sulfenyl groups proceeded in the absence of a Lewis base, with kinetic studies indicating an autocatalytic mechanism. The incorporation of electron-poor sulfenyl groups demonstrated little autocatalysis necessitating the use of a Lewis base. This method proved amenable to diverse arenes and heterocycles and was effective in the context of the late-stage functionalization of biologically active small molecules.
- Nalbandian, Christopher J.,Brown, Zachary E.,Alvarez, Erik,Gustafson, Jeffrey L.
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supporting information
p. 3211 - 3214
(2018/06/11)
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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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- Iodine-mediated sulfenylation of 4-hydroxycoumarins with sulfonyl hydrazides under aqueous conditions
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An efficient, metal-free approach to the synthesis of sulfenylated coumarins based on the iodine catalyzed regioselective sulfenylation of 4-hydroxycoumarins with arylsulfonyl hydrazides was developed under mild conditions in water. Various sulfenylated c
- Yang, Zan,Yan, Yueqiao,Li, An,Liao, Jiashu,Zhang, Lei,Yang, Tao,Zhou, Congshan
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supporting information
p. 14738 - 14741
(2018/09/29)
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- Co(II)-catalyzed regioselective clean and smooth synthesis of 2-(aryl/alkyl-thio)phenols via sp2 C-H bond activation
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The first example of a smooth, practical and useful strategy for the preparation of ortho-aryl/alkyl sulfenyl phenols by using the reaction of aryl/alkyl thiols with phenols in the presence cobalt as catalyst, and with the assistance of acetic anhydride as directing group via C-H bond activation, was developed. Described method enables to form selectively C-S bond without any ligand, oxidant, and aryl/alkyl halide under mild conditions.
- Rostami, Abed,Khakyzadeh, Vahid,Zolfigol, Mohammad Ali,Rostami, Amin
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p. 260 - 263
(2018/05/04)
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- Acid-induced chemoselective arylthiolations of electron-rich arenes in ionic liquids from sodium arylsulfinates: The reducibility of halide anions in [Hmim]Br
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An acid-induced protocol for the chemoselective arylthiolations of electron-rich arenes in ionic liquids from sodium arylsulfinates is introduced. The chemistry, in which [Hmim]Br (heaxylmethylimidazolium bromide) is used as both a solvent and a reducer, provides several advantages including odorless and simple operation, inexpensive reagents, recyclable solvents and gram-scale synthesis.
- Xu, Zhu-Bing,Lu, Guo-Ping,Cai, Chun
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supporting information
p. 2804 - 2808
(2017/04/04)
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- N-Hydroxy sulfonamides as new sulfenylating agents for the functionalization of aromatic compounds
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An unprecedented use of N-hydroxy sulfonamides as sulfenylating agents has been established. In the presence of catalytic amounts of iodine and N-hydroxysuccinimide, N-hydroxy sulfonamides participated in sulfenylation with indoles, 7-azaindole, N-methyl pyrrole, and 2-naphthol to afford structurally diverse thioethers in moderate to excellent yields with very high regioselectivity.
- Wang, Fu-Xiang,Zhou, Shao-Da,Wang, Chengming,Tian, Shi-Kai
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supporting information
p. 5284 - 5288
(2017/07/10)
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- Preparation method of aromatic sulfide compound
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The invention discloses a preparation method of an aromatic sulfide compound. The preparation method comprises adding a substrate A, a substrate B and an acid into a reactor, adding an ionic liquid as a reaction solvent into the reactor, heating and stirring the solution for a reaction, after the reaction is finished, extracting the product though an organic solvent, carrying out rotary evaporateion to remove the solvent, and carrying out column chromatography or recrystallization to obtain a product. The preparation method has the advantages that (1) the reaction occurs in the ionic liquid and the imidazole type ionic liquid as a reaction medium has a low price, low volatility and recoverability, (2) the reaction condition is mild and other metal catalysts and a reducer are not used, and (3) a yield is high, operability is strong and industrial production feasibility is obtained.
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Paragraph 0020-0022
(2017/06/02)
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- Microwave assisted synthesis of 1-(arylthio)naphthalen-2-ols and their antimicrobial activity
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A series of 1-(arylthio)naphthalen-2-ols have been synthesized by condensation of naphthalen-2-ol with 1,2-diaryldisulfanes in the presence of iodine under microwave irradiation and conventional heating methods. Structures of the products were elucidated
- Anjaiah, Ch.,Nagamani,Abraham Lincoln, Ch.,Ashok
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p. 2930 - 2932
(2018/02/21)
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- Solvent- and Metal-Free Chalcogenation of Bicyclic Arenes Using I2/DMSO as Non-Metallic Catalytic System
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We have developed a green and efficient protocol for the chalcogenation of bicyclic arenes by using I2/DMSO as catalytic system under solvent- and metal-free conditions. This protocol allows access to several chalcogenated bicyclic arenes throu
- Silva, Lais T.,Azeredo, Juliano B.,Saba, Sumbal,Rafique, Jamal,Bortoluzzi, Adailton J.,Braga, Antonio L.
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supporting information
p. 4740 - 4748
(2017/09/07)
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- Regioselective thiolation of electron rich arenes and heterocycles in recyclable catalytic media
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A convenient and novel approach has been developed for the synthesis of unsymmetrical diaryl sulfides by the reaction of sulfonyl hydrazides with phenols using a [Bmim][Br] ionic liquid through the formation of C-S bonds. The reaction has further been extended to indole, β-naphthol and aromatic amine moieties. This protocol offers a new, versatile and greener approach for thiolation of natural phenols (monoterpenes)/aromatic phenols/β-naphthols/aromatic amines and indoles without using any catalyst. A broad range of functional groups were well tolerated in this reaction system.
- Raghuvanshi, Dushyant Singh,Verma, Narsingh
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p. 22860 - 22868
(2017/07/10)
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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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- Synthetic method for aryl thioether compounds
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The invention provides a synthetic method for aryl thioether compounds. The synthetic method comprises the following steps: adding phenolic compounds or aminated compounds, thio-alcohol compounds, a transition-metal catalyst and water into a reaction bott
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Paragraph 0027; 0028; 0029; 0030
(2017/08/29)
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- Odorless, Regioselective Synthesis of Diaryl Sulfides and α-Thioaryl Carbonyls from Sodium Arylsulfinates via a Metal- Free Radical Strategy in Water
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Regioselective arylthiolations of aromatic amines, arenols and ketones via C–H bond functionalization have been achieved with I2and PPh3in an aqueous system, whereby arylsulfenyl radicals are in situ generated from odorless sodium arylsulfinates. The arylsulfenyl radicals can react with free anilines containing electron-withdrawing groups and complex substrates (estrone and progesterone). Further experiments and quantum chemical calculations were also performed to deduce a mechanism for the formation of arylsulfenyl radicals. (Figure presented.).
- Lin, Ya-Mei,Lu, Guo-Ping,Wang, Gui-Xiang,Yi, Wen-Bin
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supporting information
p. 4100 - 4105
(2016/12/30)
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- Copper-Catalyzed Three-Component One-Pot Synthesis of Aryl Sulfides with Sulfur Powder under Aqueous Conditions
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A copper-catalyzed three-component (arenes, iodohydrocarbon, and sulfur powder) synthesis of substituted aryl sulfides has been developed. Water is used as the green solvent in a simple and environmentally friendly procedure. Various functional groups attached to the substrates were well tolerated in this process to afford the corresponding products in moderate to good yields. (Figure presented.).
- Xiao, Fuhong,Chen, Shuqing,Li, Cheng,Huang, Huawen,Deng, Guo-Jun
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p. 3881 - 3886
(2016/12/16)
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- Cooperative catalysis by bovine serum albumin-iodine towards cascade oxidative coupling-C(sp2)-H sulfenylation of indoles/hydroxyaryls with thiophenols on water
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Cooperative cascade catalysis by bovine serum albumin (BSA)-iodine allows for the first time the performance of C(sp2)-H sulfenylation of indole from readily available thiophenol (-SH bond) via in situ generation/cleavage of disulfide (S-S bond
- Saima,Equbal, Danish,Lavekar, Aditya G.,Sinha, Arun K.
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supporting information
p. 6111 - 6118
(2016/07/06)
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- Iodine-mediated thiolation of phenol/phenylamine derivatives and sodium arylsulfinates in neat water
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An efficient and convenient protocol for iodine-mediated thiolation of phenols/phenylamines with sodium benzene-sulfinates in water has been achieved. In this transformation, environment-friendly conditions (including metal-free and water as solvent) are employed under air conditions, and a series of valuable thioethers are easily obtained in moderate to good yields.
- Wang, Dingyi,Zhang, Rongxing,Lin, Sen,Yan, Zhaohua,Guo, Shengmei
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p. 108030 - 108033
(2016/01/09)
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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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- Iodine-mediated thiolation of substituted naphthols/naphthylamines and arylsulfonyl hydrazides via C(sp2)-H bond functionalization
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A direct method has been developed for iodine-mediated thiolation of naphthols/naphthylamines and arylsulfonyl hydrazides through the formation of C-S bond and cleavage of S-N/S-O bonds. In this transformation, a range of valuable thioethers are easily achieved in moderate to good yields.
- Kang, Xing,Yan, Rulong,Yu, Guiqin,Pang, Xiaobo,Liu, Xingxing,Li, Xiaoni,Xiang, Likui,Huang, Guosheng
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p. 10605 - 10610
(2015/02/19)
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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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- Generation of arynes triggered by sulfoxidemetal exchange reaction of ortho-sulfinylaryl triflates
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Arynes were efficiently generated from readily available ortho-sulfinylaryl triflates by the treatment with phenylmagnesium bromide in tetrahydrofuran at 78 C. Aryne generation was initiated by a rapid sulfoxidemetal exchange reaction, followed by the immediate elimination of the ortho-OTf group. Various arynophiles efficiently reacted with arynes generated by this method within 10min, providing the corresponding adducts in high yields.
- Yoshida, Suguru,Uchida, Keisuke,Hosoya, Takamitsu
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supporting information
p. 116 - 118
(2014/01/23)
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- Vanadium-catalyzed sulfenylation of indoles and 2-naphthols with thiols under molecular oxygen
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Vanadium oxyacetylacetonate [VO(acac)2] works as a catalyst for the direct synthesis of 3-sulfanylindoles from indoles and thiols under an atmospheric pressure of molecular oxygen as a reoxidant. For example, the reaction of 2-phenylindole with benzenethiol in the presence of a catalytic amount of VO(acac)2, potassium iodide, and 2,6-di-tert-butyl-p-cresol in chlorobenzene under molecular oxygen proceeds to afford 2-phenyl-3- (phenylsulfanyl)indole in 86% yield. This catalytic system can also be applied to 2-naphthols instead of indoles to give the corresponding 1-sulfanyl-2- naphthols in up to 57% yield.
- Maeda, Yasunari,Koyabu, Motonori,Nishimura, Takahiro,Uemura, Sakae
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p. 7688 - 7693
(2007/10/03)
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