- Manganese(III) Acetate Mediated Synthesis of 3-arylsulfenylindoles and Evaluation of Their Antibacterial Activity
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The present work reports a simple and efficient method for the sulfenylation of a wide variety of indoles with aryl, benzothiazolethiols using manganese(III) acetate promoted free radical reaction. This method is selective at the C3 position of indoles and offers several advantages such as broad substrate scope, functional group tolerance (bromo, carboxylic acid, methoxy, difluoromethoxy, ester groups) and gives the required products in good to excellent yields. The experimental simplicity makes it a useful and attractive approach for the synthesis of 3-arylsulfenylindoles. The compounds 1-12 are evaluated for the anti-bacterial agents. Most of them exhibited promising activities.
- Ravi Kumar,Arumugam, Thangamani
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- Synergistic Effect of Squaric Acid in Bromine-Catalyzed Deoxygenation of Sulfonyl Derivatives: Mechanistic Investigations and Synthetic Applications in Electrophilic (Fluoroalkyl)sulfenylation
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A method for electrophilic (fluoroalkyl)sulfenylation of nucleophiles by collaborative CTAB- and squaric acid-promoted deoxygenation of sulfonyl derivatives is reported. Mechanistic studies indicate that squaric acid dramatically decreased the energy barr
- Xiang, Haonan,Liu, Jie,Wang, Jieping,Jiang, Lvqi,Yi, Wenbin
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supporting information
p. 181 - 185
(2021/12/17)
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- 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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- Cp*Co(iii)-catalyzed C2-thiolation and C2,C3-dithiolation of substituted indoles withN-(arylthio)succinimide
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A general and efficient Cp*CoIII-catalyzed C2-thiolation and C2,C3-dithiolation of indole derivatives has been achieved employingN-(aryl/alkylthio)succinimide as a thiolating reagent. This external oxidant-free method utilizes only catalytic amounts of additive and tolerates various functional groups to afford various thiolated products in good yields. Control experiments revealed the importance of the Cp*CoIII-catalyst for both C2- and C3-thiolation.
- Anbarasan, Pazhamalai,Ghorai, Jayanta,Kesavan, Arunachalam
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supporting information
p. 10544 - 10547
(2021/10/19)
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- Palladium-Catalyzed Direct C2-Biarylation of Indoles
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Biaryl and indole units are important structural motifs in several bioactive molecules and functional materials. We have accomplished straightforward access to C2-biarylated indole derivatives through palladium-catalyzed C-H activation strategy with a bro
- Murugesan, Tamilarasu,Sivarajan, Chinraj,Jayakumari, Chithra Mohan,Singh, Rajat Kumar,Vennapusa, Sivaranjana Reddy,Kaliyamoorthy, Alagiri
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supporting information
p. 10838 - 10851
(2021/08/16)
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- Multicomponent Synthesis of Sulfones and Sulfides from Triarylbismuthines and Sodium Metabisulfite in Deep Eutectic Solvents
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This study describes a novel and catalyst-free methodology for the multicomponent synthesis of a broad range of sulfones, disulfides, and sulfides from non-toxic triarylbismuthines (Ar3Bi) and sodium metabisulfite (Na2S2O5) in deep eutectic solvents (DESs). The fine tuning of the DESs properties allowed the solubility of all reagents, enhancing their reactivity, as well as, the recyclability of the reaction medium for at least 5 consecutive cycles. Thus, this versatile strategy uses non-toxic reagents without the need of metal catalysts in a sustainable solvent, being an interesting alternative to traditional hazardous protocols.
- Saavedra, Beatriz,Marset, Xavier,Guillena, Gabriela,Ramón, Diego J.
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supporting information
p. 3462 - 3467
(2020/06/04)
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- Recyclable Cellulose-Derived Fe3O4@Pd NPs for Highly Selective C–S Formation by Heterogeneously C–H Sulfenylation of Indoles
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Abstract: An efficient and convenient method was developed for the preparation of 3-sulfenylindoles via a cellulose-derived Fe3O4@Pd NPs catalyzed heterogeneously C–H sulfenylation of indoles. This approach provides an effective synthetic route to an important class of indoles derivatives and features high efficiency, easy operation, good practicality, and environmental friendliness. The recoverable catalyst was separated from the reaction mixture using an outside magnetic field and can be recycled five times without huge loss of catalytic performance. Graphic Abstract: An efficient method was developed for the preparation of 3-sulfenylindoles via cellulose-derived Fe3O4@Pd NPs catalyzed heterogeneously C–H sulfenylation of indoles.[Figure not available: see fulltext.].
- Li, Shengyi,Wang, Jinguo,Jin, Jianzhong,Tong, Jianying,Shen, Chao
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p. 2409 - 2414
(2020/02/25)
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- Triphosgene/Sodium Organosulfinate System: A General and Efficient Electrophilic Thiolation of Silylenol Ethers and Electron-Rich Heteroaromatics
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An efficient and practical approach to electrophilic thiolation was developed by using commercially available triphosgene as a reductant and the appropriate alkyl- or arylsulfinates, which were transformed in situ into electrophilic RSCl intermediates in the presence of triphosgene. This procedure represents a general and powerful approach for the synthesis of α-(trifluoromethyl)thio-substituted ketones and thiolated electron-rich heteroaromatic compounds.
- Gao, Hai-Jun,Gu, Yu-Xin,Wang, Zhe-Fei,Yuan, Yan-Qin,Wang, Yan,Guo, Sheng-Rong
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supporting information
p. 1838 - 1842
(2020/10/21)
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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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- Cuprous complex, preparation method thereof and application of cuprous complex in synthesis of 3-indolyl thioether
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The invention relates to a cuprous complex, a preparation method thereof and an application of the cuprous complex in synthesis of 3-indolyl thioether. The structural formula of the cuprous complex isshown in the specification, Ar is aryl containing a benzene ring or heterocyclic aryl, and ''.'' is a boron hydrogen bond; the preparation method comprises the following steps: 1) dissolving ortho-carborane diformaldehyde and arylamine in an organic solvent, reacting at 60-100 DEG C, and cooling to room temperature after the reaction is finished; and 2) adding CuI, reacting at room temperature for 3-6 hours, and separating to obtain the cuprous complex. Compared with the prior art, the cuprous complex containing the ortho-position carborane Schiff base ligand can efficiently catalyze the coupling reaction of synthesizing a 3-indolyl thioether compound from indole and thiophenol, the method has the advantages of high selectivity, low catalyst dosage, mild reaction conditions, open reaction(taking air as an oxidant), high reaction rate, high yield, wide substrate range and the like and shows a wide industrial application prospect.
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Paragraph 0050-0060
(2020/08/02)
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- Photocatalytic Synthesis of 3-Sulfanyl- and 1,3-Bis(sulfanyl)indolizines Mediated by Visible Light
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A metal-free method for the synthesis of 3-sulfanyl indolizines from thiols and 2-arylindolizines, is reported. The reaction is mediated by eosin Y under blue LED light irradiation and uses atmospheric oxygen as oxidant. By the use of a catalytic amount of I2, the corresponding 1,3-bis-sulfanyl indolizines are obtained, in good yields.
- Gomes, Caroline S.,Lenard?o, Eder J.,Monzon, Loana I.,Penteado, Filipe,Perin, Gelson,Silveira, Claudio C.
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supporting information
(2020/04/07)
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- ANTIMICROBIAL COMPOUNDS, COMPOSITIONS, AND ARTICLES OF MANUFACTURE FOR SELECTIVELY INHIBITING PATHOGENIC MICROBES
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A compound can have a structure of Formula A, or derivative thereof, salt thereof, or stereoisomer thereof, or having any chirality at any chiral center, or tautomer, polymorph, solvate, or combination thereof: wherein ring A is a phenyl, indolyl, naphthyl, or benzothiazolyl; X is S, SO, or SO2; Y is a linker or bond; Z is CH, CR2, or N; Z1 is C or N to form an imidazopyridine; each Z2, Z3, or Z4 is independently CH, CR2, or N; each Z5 or Z6 is C or CH; each R1, R2, and R3 is independently a substituent, and at least one of R1, R2, or R3 is a substituent other than a hydrogen; m is 0, 1, 2, 3, or 4; and n is 0 or a positive integer. The compounds can have specific substituent patterns.
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- Synthesis of Polysubstituted 3-Chalcogenated Indoles through Copper(I) Iodide-Catalyzed Three-Component Domino Reactions
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Polysubstituted 3-chalcogenated indoles were synthesized by a three-component, one-pot, domino reaction of a N -(2-bromophenyl)trifluoroacetamide, a 1-alkyne, a disulfides or diselenides, CuI, and proline in DMF. In this process, tandem Sonogashira coupling, N-cyclization, and sulfenyl/selenyl electrophilic substitution occurred sequentially and smoothly to form the anticipated products in good to excellent yields (20 examples; 65-96%). Notably, no palladium catalyst was used in this catalytic system, supporting its cost effectiveness and potential industrial application.
- Gou, Rui,Zhang, Yi,Wu, Sheng-Wei,Liu, Feng
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supporting information
p. 207 - 212
(2019/01/14)
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- Fe(III)-Catalyzed direct C3 chalcogenylation of indole: The effect of iodide ions
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A mild and efficient iron (III)-catalyzed C3 chalcogenylation of indoles has been developed and the role of the iodide ions in this transformation was investigated. EPR experiments revealed the reduction of Fe(III) to Fe(II) under the reaction conditions, supporting the formation of molecular iodine in the system, which in effect catalyze the reaction. The scope of the chalcogenylation was broad and the synthesis of more functionalized 3-selenylindoles was explored.
- Luz, Eduardo Q.,Seckler, Diego,Araújo, Janylson Souza,Angst, Leonardo,Lima, David B.,Maluf Rios, Elise Ane,Ribeiro, Ronny R.,Rampon, Daniel S.
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supporting information
p. 1258 - 1266
(2019/02/03)
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- in situ Formation of RSCl/ArSeCl and Their Oxidative Coupling with Enaminone Derivatives Under Transition-metal Free Conditions
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The reaction of diorganyl disulfides or diselenides with PhICl2 in DMF at room temperature led to the in situ formation of the reactive organosulfenyl chloride (RSCl) or selenenyl chloride (ArSeCl), which reacted with enaminone compounds to afford a series of α-thioenaminones or α-selenylenaminones, respectively, including the bioactive inhibitor for Cdc25B and its analogue, via the intermolecular oxidative C(sp2)-S/Se cross coupling reactions under metal-free conditions. (Figure presented.).
- Shang, Zhenhua,Chen, Qingyu,Xing, Linlin,Zhang, Yilin,Wait, Laura,Du, Yunfei
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supporting information
p. 4926 - 4932
(2019/11/03)
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- An electrochemical synthesized by catalytic oxidation of 3 - mercapto indole compounds
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The invention discloses a synthesizing method for a 3-mercapto indole compound through electrochemical catalytic oxidation. According to the method, a three-electrode system is used, a cathode and ananode are graphite electrodes, and a silver nitrate acetonitrile solution of 0.1mol/L is used as a reference electrode; and the indole compounds, disulfide and potassium iodide are added in a sodium tetrafluoroborate acetonitrile solution, stirring and electrolytic reaction are conducted for 3-24h under the condition of the temperature of 45-75 DEG C and 0.2-0.6 V constant voltage, a reaction solution is post-processed, and the product 3-mercapto indole compound is obtained. By means of the synthesizing method, operation is simple, convenient and safe, the yield of the product 3-mercapto indole compound is high, the reaction condition is mild, clean electrical energy is used as a redox agent, and the environmental cost is greatly reduced.
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Paragraph 0093-0094
(2019/05/16)
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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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- NH4I/1,10-phenanthroline catalyzed direct sulfenylation of N-heteroarenes with ethyl arylsulfinates
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An efficient synthesis of N-heterocyclic aryl sulfides via NH4I/1,10-phenanthroline-catalyzed direct sulfenylation reactions was reported. In this reaction, heteroarenes such as indoles, and pyrroles serve as nucleophiles by installing a arylthio group at the C3 and C2 position of heterocycles, respectively. With readily accessible and free of unpleasant odor ethyl arylsulfinates as sulfur reagents, the metal-free-catalyzed direct sulfenylation of N-heteroarenes has been developed. 3-Arylthio-indoles and 2-arylthio-pyrroles derivatives were obtained in moderate to excellent yields, even on gram scale. The reaction was general for a broad scope of substrates and demonstrated good tolerance to a variety of functional groups.
- Chen, Lingjuan,Zhang, Jun,Wei, Yueting,Yang, Zhen,Liu, Ping,Zhang, Jie,Dai, Bin
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- Multifunctionalization of Indoles: Synthesis of 3-Iodo-2-sulfonyl Indoles
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The selective multifunctionalization of indoles by using thiosulfonates, trimethyl sulfoxonium iodide (Me3SOI), and H2O2 was studied. The reaction of thiosulfonates with Me3SOI and H2O2 produced sulfonyl radicals and an iodination reagent, both of which were incorporated in indoles to form 3-iodo-2-sulfonyl indoles under carefully controlled conditions. The related reaction mechanism and the substrate scope of 3-iodo-2-sulfonyl indoles are presented.
- Park, Hyowon,Bae, Junryeol,Son, Soobin,Jang, Hye-Young
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supporting information
p. 1128 - 1133
(2019/11/22)
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- Domino C?S/C?N Bond Formation Using Well-Defined Copper-Phosphine Complex Catalyst: Divergent Approach to 3-Sulfenylated Indoles
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A protocol was developed for the synthesis of 3-thioindoles in good-to-excellent yields involving sulfenylation between 2-nitrocinnamaldehydes and various thiols using a well-defined copper(I)-phosphine complex catalyst. This unconventional divergent approach involves in situ generation of indoles via domino C?S/C?N bond formation initiated by sulfa-Michael addition followed by intramolecular N-heteroannulation. This protocol shows good chemoselectivity and broad substrate scope. To briefly demonstrate the value of this approach, 2-benzoyl-3-sulfenylated indoles were prepared from commercially available 2-nitrochalcones and thiols. (Figure presented.).
- Tamargo, Ramuel John Inductivo,Kim, Sung Hong,Lee, Yong Rok
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p. 4005 - 4015
(2019/07/18)
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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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- Organophosphorus-Catalyzed Deoxygenation of Sulfonyl Chlorides: Electrophilic (Fluoroalkyl)sulfenylation by PIII/PV=O Redox Cycling
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A method for electrophilic sulfenylation by organophosphorus-catalyzed deoxygenative O-atom transfer from sulfonyl chlorides is reported. This C?S bond-forming reaction is catalyzed by a readily available small-ring phosphine (phosphetane) in conjunction with a hydrosilane terminal reductant to afford a general entry to sulfenyl electrophiles, including valuable trifluoromethyl, perfluoroalkyl, and heteroaryl derivatives that are otherwise difficult to access. Mechanistic investigations indicate that the twofold deoxygenation of the sulfonyl substrate proceeds by the intervention of an off-cycle resting state thiophosphonium ion. The catalytic method represents an operationally simple protocol using a stable phosphine oxide as a precatalyst and exhibits broad functional-group tolerance.
- Ghosh, Avipsa,Lecomte, Morgan,Kim-Lee, Shin-Ho,Radosevich, Alexander T.
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supporting information
p. 2864 - 2869
(2019/02/01)
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- Iodine(III) Enabled Dehydrogenative Aryl C?S Coupling by in situ Generated Sulfenium Ion
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Due to the normal polarity preferences, arenes form stable complexes with thiols through S?H???π interaction and direct dehydrogenative aryl C?S coupling is usually restricted. We report here an umpolung based one pot and direct C?S coupling approach unde
- Choudhuri, Khokan,Maiti, Saikat,Mal, Prasenjit
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p. 1092 - 1101
(2019/01/30)
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- Preparation method of 3-thioether indole or 3-selenide indole
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The invention discloses a preparation method of 3-thioether indole or 3-selenide indole. The method comprises the following steps that 3-thioether indole and 3-selenide indole are synthesized by usingpotassium tert-butoxide as alkali and using an indole type compound, disulfide ether and diselenide ether as substrates in an DMF solvent. The preparation method has the advantages that the reactionraw materials are cheap and can be easily obtained; the preparation method is simple; the potassium tert-butoxide is used as alkali; reaction is performed at room temperature; the reaction time is short; the yield is high; the operation is simple; the preparation method is applicable to the synthesis of two compounds of 3-thioether indole and 3-selenide indole. The method can be used for synthetizing a series of 3-thioether indole and 3-selenide indole; the synthetized product is an active compound.
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Paragraph 0029-0031; 0034-0036; 0039-0041
(2018/10/19)
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- An efficient: T -BuOK promoted C3-chalcogenylation of indoles with dichalcogenides
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A versatile and efficient method for the synthesis of 3-chalcogenyl-indoles from indoles and dichalcogenides employing t-BuOK as a promoter at room temperature has been achieved. The present protocol exhibited a broad functional group tolerance. Diverse 3-sulfenyl- and 3-selenyl-indoles were rapidly obtained in good to excellent yields with high regioselectivities. It is noteworthy that this transformation was applicable to N-protected and N-unprotected indoles, allowing N-deprotection and C3-chalcogenylation of indoles in one step.
- Yu, Yuanzu,Zhou, Yan,Song, Zengqiang,Liang, Guang
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supporting information
p. 4958 - 4962
(2018/07/25)
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- Electrochemical sulfenylation of indoles with disulfides mediated by potassium iodide
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A novel electrochemical system for sulfenylation of indoles with disulfides to generate 3-sulfenylindoles via C-S bond formation mediated by potassium iodide at a low potential was developed. Iodine was electrogenerated from iodide ions at a graphite anode and showed a high catalytic activity for the electrochemical sulfenylation reactions. A variety of aromatic, heteroaromatic and aliphatic disulfides could react with 2-methlyindole to synthesize the corresponding 3-sulfenylindoles in good to excellent yields. In addition, protected and unprotected indoles with various groups, especially electron-donating groups, also performed well in the sulfenylation reactions. The transformation, which proceeded through the redox of iodine and the generation of intermediate 3-iodoindole, provided an efficient and environmentally benign protocol for the synthesis of 3-sulfenylindoles under mild conditions.
- Chen, Chen,Niu, Pengfei,Shen, Zhenlu,Li, Meichao
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p. G67 - G74
(2018/05/22)
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- Synthesis of 3-Sulfenylindoles from Indoles and Various Sulfenylation Agents through Aerobic Oxidative C-S Bond Coupling
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A novel aerobic catalytic oxidation system for the sulfenylation of indoles with a variety of sulfenylation agents through oxidative C-S bond coupling has been successfully developed. The reactions were performed with potassium iodide as the catalyst, sodium nitrite as the co-catalyst, and molecular oxygen as the terminal oxidant in the presence of acetic acid. Under the optimal reaction conditions, a number of indoles could be sulfenylated with Bunte salts, thiols, or disulfides to generate 3-sulfenylindoles in good yields. This protocol provided an efficient and environmentally benign strategy for the synthesis of 3-sulfenylindoles.
- Xu, Chaorong,Yi, Shanli,Li, Meichao,Hu, Xinquan,Sun, Nan,Jin, Liqun,Hu, Baoxiang,Shen, Zhenlu
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supporting information
p. 1914 - 1920
(2018/08/28)
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- Direct, Metal-free C(sp2)?H Chalcogenation of Indoles and Imidazopyridines with Dichalcogenides Catalysed by KIO3
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Herein, we report a greener protocol for the synthesis of 3-Se/S-indoles and imidazo[1,2-a]pyridines through direct C(sp2)?H bond chalcogenation of heteroarenes with half molar equivalents of different dichalcogenides, using KIO3 as a non-toxic, easy-to-handle catalyst and a stoichiometric amount of glycerol. The reaction features are high yields, based on atom economy, easy performance on gram-scale, metal- and solvent-free conditions as well as applicability to different types of N-heteroarenes.
- Rafique, Jamal,Saba, Sumbal,Franco, Marcelo S.,Bettanin, Luana,Schneider, Alex R.,Silva, Lais T.,Braga, Antonio L.
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supporting information
p. 4173 - 4180
(2018/02/06)
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- NH4I-catalyzed chalcogen(S/Se)-functionalization of 5-membered N-heteroaryls under metal-free conditions
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Herein, we described the NH4I-catalyzed C–H bond chalcogenation of N-heteroaryls in the presence of a minimum amount of DMSO/H2O/acetic acid as additives (2.5/2.5/1 M equiv., respectively), under metal-free conditions. Under optimized conditions, a wide variety of sulfenyl/selenyl imidazo[1,2-α]pyridines were prepared in very good yields. Moreover, the present approach was also highly efficient for the chalcogenation of different 5-membered N-heteroaryls, e.g., indole, imidazothiazole, indazole and imidazopyrimidine derivatives.
- Bettanin, Luana,Saba, Sumbal,Doerner, Carlos V.,Franco, Marcelo S.,Godoi, Marcelo,Rafique, Jamal,Braga, Antonio L.
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p. 3971 - 3980
(2018/06/12)
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- Catalyst-free sulfenylation of indoles with sulfinic esters in ethanol
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A novel catalyst-free method for the synthesis of structurally diverse indole thioethers in moderate to excellent yields has been developed. In this reaction, sulfinic esters serve as new sulfur electrophiles.
- Yang, Xiuqin,Bao, Yishu,Dai, Zonghao,Zhou, Qingfa,Yang, Fulai
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supporting information
p. 3727 - 3731
(2018/08/21)
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- Synthesis of a new series of Ni(II), Cu(II), Co(II) and Pd(II) complexes with an ONS donor Schiff base: Crystal structure, DFT study and catalytic investigation of palladium and nickel complexes towards deacylative sulfenylation of active methylenes and regioselective 3-sulfenylation of indoles: Via thiouronium salt formation
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A series of Ni(ii), Cu(ii), Co(ii), and Pd(ii) complexes have been synthesized with a chelating Schiff base ligand coordinated to a metal center with ONS donor atoms. The ligand and complexes are characterized by elemental analysis and spectroscopic techniques like FT-IR, 1H-NMR, and UV-Visible spectroscopy. The single crystal structure of the Pd(ii) complex is obtained by X-ray diffraction analysis and exhibits slightly distorted square planar geometry. The structure is optimized by DFT, TD-DFT calculation to elaborate the electronic structure and NBO for the charge distribution analysis of the Pd(ii) complex. The synthesized Pd(ii) and Ni(ii) complexes as catalysts have been investigated in the C-S cross-coupling of indoles and active methylenes. The metal propelled regioselective transformation afforded 3-sulfenylated indoles while β-diketones favored deacylated monosulfenyl ketones in an excellent yield via thiouronium salt formation. The Pd(ii) complex displays slightly better reactivity whereas the Ni(ii) complex is cost-efficient. The method is fast, easy to handle and cost effective in terms of high reactivity of catalysts, use of non-toxic solvents, and cheaper aryl halides and thiourea replace conventional sulfur sources, providing a practical access to organic transformations.
- Devi, Namita,Sarma, Kuladip,Rahaman, Rajjakfur,Barman, Pranjit
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p. 4583 - 4595
(2018/04/03)
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- Synthesis of 3-sulfenylindoles by Pd (II) nanoclusters confined within metal-organic framework fibers in aqueous solution
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We have found that fibrous nanosilica (KCC-1) can used as a excellent support for the synthesis of highly sparse nanoparticles. KCC-1 has high surface area that was functionalized with 1,3-bis(dimethylthiocarbamoyloxy)benzene groups acting as the strong performers so that the Pd (II) was complex without aggregation on the fibers of the KCC-1 microspheres (KCC-1/BTB/Pd). For synthesis of 3-sulfenylindoles from aryl iodide, indoles, and thiourea used from the KCC-1/BTB/Pd NPs as a catalyst that showed excellent catalytic activities under green conditions. Compared with the traditional substrate, KCC-1/BTB/Pd substantially increases protection and the accessibility of the nanoparticle sites due to its three dimensional hierarchical structure.
- Zhiani, Rahele,Sadeghzadeh, Seyed Mohsen,Emrani, Shokufe,Abasian, Maryam
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- Synergistic Cooperative Effect of Sodium borohydride-Iodine Towards Cascade C?N and C?S/Se Bond Formation: One-pot Regioselective Synthesis of 3-Sulfenyl/selenyl Indoles and Mechanistic Insight
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In this work, a new strategy to synthesize 3-sulfenyl/selenyl indole is reported wherein LC?MS reveals a novel insight into synergistic cooperative effect of NaBH4-I2 which allows cascade C?N and C?S/C?Se bond formations via reduction-nucleophilic cyclization-chalcogenylation, three steps in one-pot, towards regioselective synthesis of diverse 3-chalcogenyl indoles including 5-bromo-3-[(3,4,5-trimethoxyphenyl)thio]-1H-indole, a known lead anticancer compound, directly from 2-amino-phenacylchlorides and thiophenols or disulfides/diselenides in aqueous dioxane under transition-metal-free condition. (Figure presented.).
- Lavekar, Aditya G.,Equbal, Danish,Saima,Sinha, Arun K.
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p. 180 - 185
(2018/01/12)
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- 3 - Mercapto of indole compounds synthesized by catalytic oxidation method (by machine translation)
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The invention discloses a 3 - mercapto of indole compounds synthesized by catalytic oxidation method, to indole compounds and sulfur on behalf of the sulfate as the substrate of reaction, to potassium iodide and sodium nitrite as catalyst, in order to acetic acid as an auxiliary agent, in order to oxygen as the oxidizing agent, the reaction substrate in the organic solvent, for normal pressure, temperature 50 - 80 °C reaction under the condition of, after the reaction is completed after the separation and processed to obtain the 3 - mercapto-indole compounds. The synthesizing method of the invention, simple and safe operation, in order to clean the oxygen as terminal oxidant, thereby greatly reducing the environmental costs; mild reaction conditions. (by machine translation)
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Paragraph 0104; 0105; 0107
(2018/10/11)
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- Metal Free Mono- and 2,3-Bis-sulfenylation of Indoles in Water with Sodium Sulfinates as a Sulfur Source
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An iodine-PPh3 mediated sulfenylation of indoles in water with stable and odorless sodium sulfinates as the sulfur source is described. The reaction could afford monosulfenylated indoles in moderate to excellent yields under metal free conditions. Moreover, double C—H sulfenylation of indoles at 2- and 3-positions has also been achieved by using excess sodium sulfinates under the optimized reaction conditions.
- Liu, Changqing,Fan, Jian,Wu, Manyi,Chen, Jiahui,Zhao, Yiming,Xie, Meihua
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p. 819 - 825
(2018/07/30)
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- Green indole compound vulcanization method with triphosgene as reducing agent
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The invention discloses a green indole compound vulcanization method with triphosgene as a reducing agent. The method comprises the following steps: by taking indole and a derivative thereof as substrate, fluomethane sodium methanesulfinate, methyl sodium methanesulfinate, cyclopropyl sodium methanesulfinate or aryl sodium methanesulfinate as a vulcanization agent, triphosgene as a reducing agent,and acetonitrile as a solvent, stirring for 2 hours in an ice bath, carrying out TLC (Thin Layer Chromatography) reaction tracking, and after sufficient reactions are completed, carrying out column chromatography isolation, so as to obtain various indole vulcanization compounds. By adopting the method disclosed by the invention, the triphosgene is adopted as the reaction reducing agent, thiophenol and dithioether with serious smell is avoided, an expensive electrophilic trifluoromethyl sulfide reagent is avoided, and a phosphorous reducing agent which can do harm to the environment can be also avoided. Till now, the indole vulcanization method is not reported yet, the preparation method is simple and convenient, low in cost and high in yield, products can be directly prepared without anytransition metal catalyst or aid, and very high practical popularization values can be achieved.
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Paragraph 0135; 0136; 0137; 0138; 0139
(2018/10/11)
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- Flavin-iodine coupled organocatalysis for the aerobic oxidative direct sulfenylation of indoles with thiols under mild conditions
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A unique coupled redox organocatalysis system using flavin and iodine catalysts efficiently promoted the metal-free aerobic oxidative direct sulfenylation of indoles with thiols at ambient temperature without any sacrificial reagents, except environmentally benign molecular oxygen. Biomimetic flavin catalysis plays multiple roles in aerobic oxidative transformations, not only regenerating I2 from in situ generated I-, but also converting thiols into disulfides.
- Ohkado, Ryoma,Ishikawa, Tatsuro,Iida, Hiroki
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supporting information
p. 984 - 988
(2018/03/13)
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- Nitrosonium ion catalysis: aerobic, metal-free cross-dehydrogenative carbon-heteroatom bond formation
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Catalytic cross-dehydrogenative coupling of heteroarenes with thiophenols and phenothiazines has been developed under mild and environmentally benign reaction conditions. For the first time, NOx+ was applied for catalytic C-S and C-N bond formation. A comprehensive scope for the C-H/S-H and C-H/N-H cross-dehydrogenative coupling was demonstrated with >60 examples. The sustainable cross-coupling conditions utilize ambient oxygen as the terminal oxidant, while water is the sole by-product.
- Bering, Luis,D'Ottavio, Laura,Sirvinskaite, Giedre,Antonchick, Andrey P.
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supporting information
p. 13022 - 13025
(2018/11/23)
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- Iron-catalyzed carbon–sulfur bond formation: Atom-economic construction of thioethers with diaryliodonium salts
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Diaryliodonium salts are characterized by poor atom economy with the formation of one equivalent of an iodoarene as waste. We have developed an atom-economic iron-catalyzed protocol for the synthesis of a variety of thioethers with diaryliodonium salts. Not only cyclic diaryliodonium salts but also linear diaryliodonium salts were found to perform well in the reactions.
- Liu, Li,Qiang, Jian,Bai, Shuhua,Li, Yang,Li, Jian
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p. 2365 - 2371
(2017/09/30)
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- Combined experimental/theoretical study on d-glucosamine promoted regioselective sulfenylation of indoles catalyzed by copper
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A combined experimental/theoretical investigation on the d-glucosamine promoted sulfenylation of indoles at the C3 position with sodium sulfinates catalyzed by copper is presented. The C3-sulfenylation of indoles shows good functional-group tolerance and yields. The 3-I-indole was identified as a crucial intermediate in the catalytic cycle. The catalytic role of [Cu(DMSO)2]2+ was addressed using quantum chemical calculations. In the interaction of [Cu(DMSO)2]2+ with indole, the [Cu(DMSO)2]2+ complex abstracts a hydrogen from the C3 of indole. The electronic origin for selective C-H bond activation of indole was revealed.
- Ge, Xin,Sun, Fengli,Liu, Xuemin,Chen, Xinzhi,Qian, Chao,Zhou, Shaodong
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p. 13175 - 13180
(2017/11/06)
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- Silver-mediated sulfenylation of indoles and benzimidazoles with di(hetero)aryl disulfides
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An efficient synthesis of novel sulfenylated N-heterocycles derivatives via AgNO3 mediated C-S coupling reaction has been developed. This reaction could be carried out under mild reaction conditions with straightforward operation and good yield
- Wang, Wen-Juan,Wang, Xi-Cun
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p. 449 - 464
(2017/05/02)
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- Visible-light promoted synthesis of 3-arylthioindoles from indoles and diaryl disulfides
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3-Arylthioindoles could be synthesized in good yields via the photoirradiation of indoles and disulfides. The reaction is efficiently promoted by the catalytic amount of sodium iodide. A reaction mechanism involving the electrophilic substitution of indol
- Ye, Lin-miao,Chen, Jie,Mao, Peng,Zhang, Xue-jing,Yan, Ming
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supporting information
p. 2743 - 2746
(2017/06/23)
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- C3 Sulfenylation of N-Heteroarenes in Water under Catalyst-Free Conditions
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A method for the catalyst-free C–H sulfenylation of imidazo[1,2-a]pyridines by using sulfonothioates as an odorless thioarylated reagent in aqueous medium was developed. This protocol was used for a variety of substituted imidazo[1,2-a]pyridines with broad functional-group tolerance and was extended to the sulfenylation of indoles and imidazothiazoles. The sulfonothioates were activated exclusively in aqueous medium rather than in an organic solvent, and the feasibility of the process for scale-up studies was demonstrated.
- Ravi, Chitrakar,Joshi, Abhisek,Adimurthy, Subbarayappa
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supporting information
p. 3646 - 3651
(2017/07/22)
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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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- A conjugate Lewis base-Br?nsted acid catalyst for the sulfenylation of nitrogen containing heterocycles under mild conditions
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Catalysts that contain a thiourea tethered to a carboxylic acid were found to affect the sulfenylation of indoles and other N-heterocycles on the hour time scale at room temperature. The mild nature of these conditions allowed for the incorporation of diverse functionalities into more complex heterocycles.
- Nalbandian, Christopher J.,Miller, Eric M.,Toenjes, Sean T.,Gustafson, Jeffery L.
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supporting information
p. 1494 - 1497
(2017/02/05)
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- Deep Eutectic Solvents as Reaction Media for the Palladium-Catalysed C?S Bond Formation: Scope and Mechanistic Studies
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A unique jigsaw catalytic system based on deep eutectic solvents and palladium nanoparticles where C?S bonds are formed from aryl boronic acids and sodium metabisulfite, is introduced. The functionalization step is compatible with a broad spectrum of reagents such as nucleophiles, electrophiles or radical scavengers. This versatile approach allows the formation of different types of products in an environmentally friendly medium by selecting the components of the reaction, which engage one with another as pieces in a jigsaw. This simple procedure avoids the use of toxic volatile organic solvents allowing the formation of complex molecules in a one-pot reaction under mild conditions. Despite the fact that only 1 mol % of metal loading is used, the recyclability of the catalytic system is possible. Kinetic experiments were performed and the reaction order for all reagents, catalyst and ligand was determined. The obtained results were compared to palladium nanocrystals of different known shapes in order to shed some light on the properties of the catalyst.
- Marset, Xavier,Guillena, Gabriela,Ramón, Diego J.
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supporting information
p. 10522 - 10526
(2017/08/10)
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- TBAI-mediated regioselective sulfenylation of indoles with sulfonyl chlorides in one pot
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A versatile method for the synthesis of 3-sulfenylated indoles via TBAI promoted sulfenylation of indoles with sulfonyl chlorides in one pot has been presented. This system features highly regioselective, metal-free, easy operation, and shows a broad functional group tolerance leading to excellent yields. And this reaction could be easily conducted in 10 mmol scale with high effectivity. A plausible mechanism is proposed.
- He, Yongzhao,Jiang, Jun,Bao, Wenhu,Deng, Wei,Xiang, Jiannan
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p. 4583 - 4586
(2017/11/15)
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- Iodine-Catalyzed Mono- and Disulfenylation of Indoles in PEG400 through a Facile Microwave-Assisted Process
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An iodine-catalyzed versatile and green method for the synthesis of mono- and 2,3-disulfenylindoles was developed. Various indoles reacted with sodium alkyl- and arylsulfinates by using hydrogen peroxide as the oxidizing agent in PEG400 under microwave conditions. This simple method enabled the rapid synthesis of mono- and 2,3-disulfenylindoles in good to excellent yields under metal-free conditions. Furthermore, this protocol is environmentally friendly, odorless, and operationally easy and can be performed within short reaction times under mild reaction conditions with excellent functional-group tolerance.
- Rahaman, Rajjakfur,Barman, Pranjit
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supporting information
p. 6327 - 6334
(2017/11/21)
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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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- Preparation method for polysubstituted indole derivatives
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The invention provides a preparation method for polysubstituted indole derivatives. The preparation method comprises employing alkynyl-terminated hydrocarbon, a halogenated aniline derivative and a disulfide as initial raw materials, using an amino acid as an additive and a copper salt as a catalyst, performing a coupling-tandem one-pot reaction in an organic solvent under an alkali-added condition, so as to obtain the corresponding polysubstituted indole derivative, wherein the catalyst is CuX, and X is iodine or bromine. According to the technical scheme, the method for synthesizing the polysubstituted indole derivatives through one-pot process is developed on the basis of a method for synthesizing 2-substituted indole through copper catalysis. The method does not employ an expensive palladium catalyst easily polluting environment. The method enables alkynyl-terminated hydrocarbon, one halogenated aniline derivative and one disulfide to have the coupling-tandem one-pot reaction under a relatively mild condition, is simple in technology and strong in operationality, and possesses industrial application prospect.
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Paragraph 0028-0030
(2017/01/19)
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