- A reusable polystyrene-supported copper(II) catalytic system for N-arylation of indoles and Sonogashira coupling reactions in water
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A polymer-anchored Cu(II) N,N-dimethylethylenediamine complex was prepared and characterized by various techniques, including Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), atomic absorption spectroscopy (AAS), and thermogravimetric analysis (TGA). This heterogeneous Cu(II) catalyst, efficiently works for the N-arylation of indoles and Sonogashira coupling of terminal alkynes with aryl halides in aqueous medium. The effect of solvent, and base for the C-N, and C-C coupling reactions were reported. Further, the catalyst can be easily recovered quantitatively by simple filtration and reused up to four times without significant loss of its catalytic activity.
- Kodicherla, Balaswamy,Perumgani C., Pullaiah,Mandapati, Mohan Rao
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- Synthesis of 1-aryl indoles via coupling reaction of indoles and aryl halides catalyzed by CuI/metformin
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Ullmann-type C-N coupling reaction has been developed for the synthesis of 1-aryl indole derivatives by indoles and aryl halides in the presence of CuI/metformin (CuI/Met) in DMF. This method is very easy, rapid, and high yielding reaction for the synthesis of 1-aryl indoles. In particular, the metformin, which is used as ligand, is inexpensive and nontoxic that is considered to be relatively environmentally benign.
- Chen, Hu,Lei, Min,Hu, Lihong
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- Aqueous copper-catalyzed N-arylation of indoles: The surfactant strategy
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Surfactants have long been underestimated in synthetic organic chemistry despite their great potential in promoting solubility, reactivity and selectivity in metal-mediated cross-couplings. In this study the strategy of surfactant promotion was exemplified in copper-catalyzed N-arylation of indoles in water. The different effects of surfactants during the coupling reaction were first explored. The superior promoting effect of the natural zwitterionic surfactant, betaine, was found and attributed to the capability of the formed complex to stabilize the copper intermediate in the catalytic transformation and facilitate transportation of the reactants. The concept of surfactant promotion through complexation is valuable in metal-mediated cross-couplings. This method also exhibited good recycling ability. This study will greatly facilitate exploration of surfactant promotion in metal-mediated cross-couplings.
- Liu, Songbai,Zhou, Jiahui
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- Tandem C-H Transformations by a Single Iridium Catalyst: Direct Access to Indoles and Indolines from o-Alkyl-N-methylanilines
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In the presence of an iridium catalyst bearing DTBM-SEGPHOS as a ligand and tert-butylethylene as a hydrogen scavenger, 2-ethyl-N-methylanilines were converted directly to 3-methylindoles in high yields. The reaction proceeded efficiently in mesitylene at 150 °C through transfer dehydrogenation of the ethyl group and following intramolecular dehydrogenative C-H/C-H coupling of the N-methyl group with the vinyl group formed in situ. The iridium catalyst system was applied to the asymmetric conversion affording enantioenriched indolines bearing a quaternary stereogenic carbon center at the C3 position.
- Ohmura, Toshimichi,Yagi, Kaito,Kusaka, Satoshi,Suginome, Michinori
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- COPPER CATALYSED PHENYLATION OF INDOLES BY TRIPHENYLBISMUTH BIS TRIFLUOROACETATE
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Indoles are C(3)- or N-phenylated by triphenylbismuth bis-fluoroacetate under copper catalysis.C(3)-Phenyl derivatives are obtained with C(3)-unsubstituted indoles and N-phenyl derivatives with C(3)-substituted indoles.
- Barton, Derek H. R.,Finet, Jean-Pierre,Khamsi, Jamal
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- An efficient, mild and selective Ullmann-type N-arylation of indoles catalysed by Pd immobilized on amidoxime-functionalized mesoporous SBA-15 as heterogeneous and recyclable nanocatalyst
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A wide range of N-arylated indoles were selectively synthesized through intermolecular C(aryl)-N bond formation from the corresponding aryl iodides and indoles through Ullmann-type coupling reactions in the presence of a catalytic amount of Pd immobilized on amidoxime-functionalized mesoporous SBA-15 (SBA-15/AO/Pd(0)) under mild reaction conditions. These cross-coupled products were obtained in excellent yields under mild conditions at extremely low palladium loading (ca 0.3 mol%), and the heterogeneous catalyst can be readily recovered by simple filtration and reused seven times with loss in its activity.
- Ghorbani-Vaghei, Ramin,Hemmati, Saba,Hamelian, Mona,Veisi, Hojat
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- L-Arginine as a base and ligand for the palladium-catalyzed C-C and C-N cross-coupling reactions in aqueous media
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L-Arginine (2-amino-5-guanidinopentanoic acid) acts as a base and ligand in reaction medium, exhibits a very high activity and recyclability to palladium-catalyzed C-C and C-N cross-coupling reactions in aqueous media. The corresponding Suzuki products were obtained in good to excellent yields by using various aryl halides (I, Br, Cl). Also, the cross coupling reactions of arylboronic acids with various amines in aqueous medium proceed in good to excellent yield under same conditions. Furthermore, the catalyst could be easily separated from the reaction mixture and could be recycled several times without significant loss in its catalytic activity.
- Veisi, Hojat,Mohammadi Biabri, Parisa,Falahi, Homeyra
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- Base-promoted SNAR reactions of fluoro- And chloroarenes as a route to N-aryl indoles and carbazoles
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KOH/DMSO-promoted C-N bond formation via nucleophilic aromatic substitution (SNAr) between chloroarenes or fluoroarenes with indoles and carbazole under transition metal-free conditions affording the corresponding N-arylated indoles and carbazoles has been developed.
- Iqbal, Muhammad Asif,Mehmood, Hina,Lv, Jiaying,Hua, Ruimao
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- Transition-Metal-Free N-Arylation of Amines by Triarylsulfonium Triflates
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A simple and efficient method for transition-metal-free N-arylation of various amines by triarylsulfonium triflates is described. Both aliphatic and aromatic amines were smoothly converted at 80 °C in the presence of tBuOK or KOH to give the corresponding mono N-arylated products in good to high yields. The molar ratios of the reactants and the choice of bases had a big effect on the reaction. When a large excess of [Ph3S][OTf] and tBuOK were employed for primary amines under the standard conditions, the bis(N-phenyl) products were predominantly formed. This method was also applicable to the synthesis of bioactive N-phenyl amino acid derivatives. The control experiments, the deuterium labelling study, and the presence of regioisomers of N-arylated products when using 4-substituted triarylsulfonium triflates suggested that the reaction might proceed through an aryne intermediate. The present protocol demonstrated that triarylsulfonium salts are versatile arylation reagents in the construction of CAr?N bonds.
- Tian, Ze-Yu,Ming, Xiao-Xia,Teng, Han-Bing,Hu, Yu-Tian,Zhang, Cheng-Pan
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supporting information
p. 13744 - 13748
(2018/09/14)
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- Tert-Butyl Iodide Mediated Reductive Fischer Indolization of Conjugated Hydrazones
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A novel reductive Fischer indolization of readily available N-aryl conjugated hydrazones with tert-butyl iodide has been developed. In this reaction, tert-butyl iodide is used as anhydrous HI source, and the generated HI acts as a Br?nsted acid and a reducing agent. This operationally simple method allows access to various indole derivatives. Furthermore, the procedure can be applied to the synthesis of biologically active compounds.
- Ito, Yuta,Ueda, Masafumi,Takeda, Norihiko,Miyata, Okiko
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supporting information
p. 2616 - 2619
(2016/02/26)
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- Copper nanoparticle decorated organically modified montmorillonite (OMMT): An efficient catalyst for the N-arylation of indoles and similar heterocycles
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A highly active ligand-free and efficient copper nanoparticle decorated OMMT catalyzed N-arylation of NH-heterocycles, i.e. indole, imidazole, benzimidazole, pyrrole, carbazole has been demonstrated.
- Talukdar, Dhrubajyoti,Das, Gautam,Thakur, Suman,Karak, Niranjan,Thakur, Ashim J.
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p. 238 - 243
(2015/02/19)
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- Copper-catalyzed synthesis of N-aryl and N-sulfonyl indoles from 2-vinylanilines with O2 as terminal oxidant and TEMPO as cocatalyst
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A copper-catalyzed intramolecular alkene oxidative amination that utilizes TEMPO as cocatalyst and O2 as the terminal oxidant has been developed. The method furnishes N-aryl and N-sulfonyl indoles from N-aryl and N-sulfonyl 2-vinylanilines, res
- Liwosz, Timothy W.,Chemler, Sherry R.
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supporting information
p. 335 - 339
(2015/02/19)
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- C-N coupling of indoles and carbazoles with aromatic chlorides catalyzed by a single-component NHC-nickel(0) precursor
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A new and efficient nickel-based protocol for the N-arylation of indoles and carbazoles with aromatic chlorides, the least expensive of the aryl halides, is described. The procedure provides selectively N-(hetero)arylation products in good to high yields, in short reaction times and without adding an excess of ligands.
- Rull, Silvia G.,Blandez, Juan F.,Fructos, Manuel R.,Belderrain, Tomás R.,Nicasio, M. Carmen
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supporting information
p. 907 - 911
(2015/03/30)
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- Palladium nanoparticles supported on modified single-walled carbon nanotubes: A heterogeneous and reusable catalyst in the Ullmann-type N-arylation of imidazoles and indoles
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Air- and moisture-stable and recyclable palladium nanoparticles supported on modified single-walled carbon nanotubes (SWCNT-Met/Pd) behave as very efficient heterogeneous catalysts in the Ullmann coupling of imidazoles and indoles with aryl iodides to afford the corresponding C-N coupling reactions under aerobic conditions. These cross coupled products were produced in excellent yields at low palladium loading (~0.2 mol%) and the heterogeneous catalyst can be readily recovered by simple filtration and reused five times without a noticeable loss in its catalytic activity.
- Veisi, Hojat,Morakabati, Nekoo
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p. 2901 - 2907
(2015/04/14)
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- SBA-15-functionalized melamine-pyridine group-supported palladium(0) as an efficient heterogeneous and recyclable nanocatalyst for N-arylation of indoles through Ullmann-type coupling reactions
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SBA-15-functionalized melamine-pyridine group-supported palladium(0) was found to serve as a heterogeneous and recyclable nanocatalyst for N-arylation of indoles with aryl iodides under a low catalyst loading (0.3mol% of Pd) through Ullmann-type C£N coupling reactions. A variety of aryl iodides could be aminated to provide the N-arylated products in good to excellent yields without the need of an inert atmosphere. Also, this catalyst was found to be an efficient system for the N-arylation of other nitrogen-containing heterocycles with aryl iodides. The heterogeneous palladium catalyst could be recovered by simple filtration of the reaction solution and reused for six cycles without significant loss in its activity.
- Veisi, Hojat,Poor Heravi, Mohammad Reza,Hamelian, Mona
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p. 334 - 337
(2015/04/27)
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- Palladium on carbon-catalyzed one-pot N-arylindole synthesis: Intramolecular aromatic amination, aromatization, and intermolecular aromatic amination
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Indole and indoline derivatives were selectively and temperature dependently synthesized via the intramolecular cross-coupling reaction between the amino and aromatic bromine functionalities of 2-bromophenethylamine derivatives in the presence of 10% palladium on carbon (Pd/C), 1,1-bis(diphenylphosphino)ferrocene (DPPF), and sodium tert-butoxide (NaO-t-Bu) in mesitylene at 140 and 200°C, respectively. The neutralization using acetic acid after formation of the indoline derivatives effectively promoted their aromatization, and the corresponding indole derivatives were obtained at 140°C. Furthermore, various aryl groups were also introduced to the N-1 position of the indole, pyrrole, and carbazole rings by their direct intramolecular arylation with aryl halides and a one-pot protocol for N-arylindole synthesis from 2-bromophenethylamine was developed.
- Monguchi, Yasunari,Marumoto, Takahisa,Takamatsu, Haruki,Sawama, Yoshinari,Sajiki, Hironao
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supporting information
p. 1866 - 1872
(2014/06/09)
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- N-arylation of indoles with aryl halides using copper/glycerol as a mild and highly efficient recyclable catalytic system
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A simple, efficient, and inexpensive copper catalyzed protocol has been developed for cross-coupling of indoles with aryl halides by using glycerol as a green recyclable solvent and DMSO as an additive. The reaction was carried out at low catalyst loading furnishing various N-aryl indoles in good to excellent yield. This copper/glycerol mixture was recycled up to four runs without any loss in its catalytic activity.
- Yadav, Dilip Kumar T.,Rajak, Sanil S.,Bhanage, Bhalchandra M.
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p. 931 - 935
(2014/02/14)
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- N-arylation of indoles with aryl halides using copper/glycerol as a mild and highly efficient recyclable catalytic system
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A simple, efficient, and inexpensive copper catalyzed protocol has been developed for cross-coupling of indoles with aryl halides by using glycerol as a green recyclable solvent and DMSO as an additive. The reaction was carried out at low catalyst loading furnishing various N-aryl indoles in good to excellent yield. This copper/glycerol mixture was recycled up to four runs without any loss in its catalytic activity.
- Yadav, Dilip Kumar T.,Rajak, Sanil S.,Bhanage, Bhalchandra M.
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p. 931 - 935
(2015/02/19)
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- Ligand-free Ullmann-type C-heteroatom couplings under practical conditions
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A new practical ligand-free protocol for copper-catalyzed C-heteroatom cross-coupling reactions (Ullmann-type) is described. The use of dimethyl sulfoxide (DMSO) as the solvent overcomes the need to use organic auxiliary ligands; thus, DMSO is revealed as a nontoxic and superior solvent for Ullmann-type coupling reactions. This method allows the arylation of a wide range of amides, alcohols, and amines under practical conditions with bromobenzene and iodobenzene derivatives and will likely find direct application in current organic synthesis. The competitive reactivity among different functional groups is reported and rationalized, and the possibility to achieve selective arylation reactions is demonstrated. Copyright
- Gueell, Imma,Ribas, Xavi
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p. 3188 - 3195
(2014/06/09)
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- Copper-catalyzed oxidative amination and allylic amination of alkenes
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Enamines and enamides are useful synthetic intermediates and common components of bioactive compounds. A new protocol for their direct synthesis by a net alkene C-H amination and allylic amination by using catalytic Cu II in the presence of MnO2 is reported. Reactions between N-aryl sulfonamides and vinyl arenes furnish enamides, allylic amines, indoles, benzothiazine dioxides, and dibenzazepines directly and efficiently. Control experiments further showed that MnO2 alone can promote the reaction in the absence of a copper salt, albeit with lower efficiency. Mechanistic probes support the involvement of nitrogen-radical intermediates. This method is ideal for the synthesis of enamides from 1,1-disubstituted vinyl arenes, which are uncommon substrates in existing oxidative amination protocols. A new protocol for the direct synthesis of enamides and allylic amines by oxidative N-H/C-H coupling of N-sulfonylanilines with vinylarenes is presented. The reaction works in both inter- and intramolecular modes and is catalyzed by copper salts by using MnO2 as the stoichiometric oxidant (see scheme). Nitrogen heterocycles including indoles, benzothiazine dioxides, and dibenzazepines can be formed. Copyright
- Liwosz, Timothy W.,Chemler, Sherry R.
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supporting information
p. 12771 - 12777
(2013/10/01)
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- A versatile approach to ullmann C-N couplings at room temperature: New families of nucleophiles and electrophiles for photoinduced, copper-catalyzed processes
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The use of light to facilitate copper-catalyzed cross-couplings of nitrogen nucleophiles can enable C-N bond formation to occur under unusually mild conditions. In this study, we substantially expand the scope of such processes, establishing that this approach is not limited to reactions of carbazoles with iodobenzene and alkyl halides. Specifically, we demonstrate for the first time that other nitrogen nucleophiles (e.g., common pharmacophores such as indoles, benzimidazoles, and imidazoles) as well as other electrophiles (e.g., hindered/deactivated/heterocyclic aryl iodides, an aryl bromide, an activated aryl chloride, alkenyl halides, and an alkynyl bromide) serve as suitable partners. Photoinduced C-N bond formation can be achieved at room temperature using a common procedure with an inexpensive catalyst (CuI) that does not require a ligand coadditive and is tolerant of moisture and a variety of functional groups.
- Ziegler, Daniel T.,Choi, Junwon,Munoz-Molina, Jose Maria,Bissember, Alex C.,Peters, Jonas C.,Fu, Gregory C.
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supporting information
p. 13107 - 13112
(2013/09/24)
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- Benzotriazol-1-ylmethanol: An excellent bidentate ligand for the copper/palladium-catalyzed C-N and C-C coupling reaction
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An efficient benzotriazole based N,O bidentate ligands for the Cu-catalyzed N-arylation of π-excessive nitrogen heterocycles is described. This ligand accomplishes C-N coupling of Nheterocycles and C-C coupling of boronic acids with a variety of hindered, functionalized aryl/heteroaryl halides under mild reaction conditions in good to excellent yields. Using his ligand C-N and C-C (Suzuki) couplings with bromoarenes could be conducted with less catalyst loading. A wide array of deactivated and hindered aryl halides react cleanly to afford the functionalized biaryl derivatives in high yields. ARKAT-USA, Inc.
- Jha, Rajeev R.,Singh, Jaspal,Tiwari, Rakesh K.,Verma, Akhilesh K.
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p. 228 - 248
(2013/02/23)
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- Practical copper-catalyzed N-arylation of amines with 20% aqueous solution of n-Bu4NOH
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N-Arylation of a wide variety of amines with phenylboronic acid catalyzed by copper acetate under 20% aqueous solution of n-Bu4NOH was accomplished in good to excellent yields (up to 92%) and substrate conversions (up to 96%).
- Molaei, Hamidreza,Ghanbari, Mohammad Mehdi
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experimental part
p. 301 - 304
(2012/05/05)
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- Palladium-catalyzed indole, pyrrole, and furan arylation by aryl chlorides
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The palladium-catalyzed direct arylation of indoles, pyrroles, and furans by aryl chlorides has been demonstrated. The method employs a palladium acetate catalyst, 2-(dicyclohexylphosphino)-biphenyl ligand, and an inorganic base. Electron-rich and electron-poor aryl chlorides as well as chloropyridine coupling partners can be used, and arylated heterocycles are obtained in moderate to good yields. Optimization of base, ligand, and solvent is required for achieving best results.
- Nadres, Enrico T.,Lazareva, Anna,Daugulis, Olafs
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supporting information; experimental part
p. 471 - 483
(2011/04/15)
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- Benzotriazole: an efficient ligand for the copper-catalyzed N-arylation of indoles
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A general, efficient, and inexpensive method for the N-arylation of indoles using a catalytic system derived from CuI and benzotriazole is reported. Selective mono N-arylation of indoles with ortho-dihaloarenes has also been successfully achieved in good yields using this protocol.
- Verma, Akhilesh Kumar,Singh, Jaspal,Larock, Richard C.
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scheme or table
p. 8434 - 8439
(2009/12/26)
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- Synthesis of 1-aryl-1H-indole derivatives by iodine-mediated cyclization of 2-(arylamino)styrene derivatives
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A convenient synthetic method for 1-aryl-1H-indole derivatives has been developed. 2-(Arylamino)-α-methylstyrene derivatives were treated with iodine in the presence of sodium hydrogencarbonate to give 1-aryl-3-methyl-1H- indole derivatives in fair to goo
- Kobayashi, Kazuhiro,Miyamoto, Kazuna,Yamase, Tohru,Nakamura, Daizo,Morikawa, Osamu,Konishi, Hisatoshi
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p. 1580 - 1584
(2007/10/03)
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- 2-(2-Haloalkenyl)-aryl halides as substrates for palladium-catalysed tandem C-N bond formation: Efficient synthesis of 1-substituted indoles
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2-(2-Haloalkenyl)-aryl halides, conveniently prepared in a single step from the corresponding o-halobenzaldehydes, are combined with amines under Pd catalysis to provide 1-substituted indoles. All combinations of Br and Cl leaving groups can be employed,
- Willis, Michael C.,Brace, Gareth N.,Findlay, Thomas J. K.,Holmes, Ian P.
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p. 851 - 856
(2007/10/03)
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- Thermal decomposition of tert-butyl o-(phenoxy)- and o-(anilino)-phenyliminoxyperacetates
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Some o-phenoxy- and o-anilino-substituted aryliminyl radicals have been generated by thermal decomposition of suitable tert-butyl iminoxyperacetates. The iminyls show no disposition to give 7-membered cyclisation on the phenyl group. In some cases, products have been found that can be rationalised through a 1,6-spirocyclisation of the iminyl radicals followed by homolytic 1,5-migration of the phenyl group from the aminic to the iminic nitrogen: this seems to be the first instance of such a process. Evidence has been found for the formation of imines through hydrogen abstraction by the iminyls; with two o-phenoxy-substituted peresters these imines have been unexpectedly isolated. The reactions have also afforded significant - in some cases major - amounts of other products (acridine, quinazolinone and indole derivatives) presumably deriving from carbon radicals: mechanisms are suggested to account for the formation of these compounds. The structure of the quinazolinone compound has been determined by X-ray crystallographic analysis.
- Calestani, Gianluca,Leardini, Rino,McNab, Hamish,Nanni, Daniele,Zanardi, Giuseppe
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p. 1813 - 1824
(2007/10/03)
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- Rearrangement of 1-Arylindoles to 5H-Dibenzazepines
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An unusual acid-catalyzed rearrangement of 1-arylindoles 1 to 5H-dibenzazepines 2 has been discovered.It can be used for the preparation of 2.The influence of the nature and the position of the substituents in the initial molecule 1 on the rearrangement is discussed.A possible mechanism of the reaction is suggested.A convenient method for preparation of 1-arylindoles 1c-k by means of arylation of 1-unsubstituted indoles with aryl halides by the Ullmann reaction is described.
- Tokmakov, Gennadii P.,Grandberg, Igor I.
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p. 2091 - 2098
(2007/10/02)
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- Novel Route to 4,5,6,7-Tetrahydroindoles and Pyrroles
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Treatment of cyclic unsaturated amides, 1,4,5,6,7,7a-hexahydro-2H-indol-2-ones 1, with Lawesson's reagent yielded unexpected products, 4,5,6,7-tetrahydroindoles 2, in moderate yield.Re
- Nishio, Takehiko,Okuda, Norikazu,Kashima, Choji
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p. 899 - 902
(2007/10/02)
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- 154. Reduction of Indolin-2-ones and Desulfurization of Indoline-2-thiones to Indoline and Indole Derivatives
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Reduction of indolin-2-ones with lithium aluminium hydride (LAH) or diisobutylaluminium hydride (DIBAL) and desulfurization of indoline-2-thiones with Raney-Ni were investigated.Treatment of indolin-2-ones 1 with LAH or DIBAL yielded indoles 4 and/or indolines 3 in moderate-to-high yields depending on the substituents at N and C(3) of 1.Indoline-2-thiones 2 were desulfurized with Raney-Ni tigive indoles 4 and/or indolines 3.
- Nishio, Takehiko,Okuda, Norikazu,Kashima, Choji
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p. 1719 - 1723
(2007/10/02)
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