- Copper-Mediated One-Pot Synthesis of Indoles through Sequential Hydroamination and Cross-Dehydrogenative Coupling Reaction
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Starting from simple anilines and ester arylpropiolates, an efficient one-pot synthesis of 2-arylindole-3-carboxylate derivatives has been developed through copper-mediated sequential hydroamination and cross-dehydrogenative coupling (CDC) reaction. The i
- Cai, Yichao,Chen, Chunxia,Chen, Xin,Liu, Yajie,Peng, Jinsong,Song, Zirui,Sun, Peng,Yang, Jiaojiao
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- Copper(ii)-catalyzed synthesis of multisubstituted indoles through sequential Chan-Lam and cross-dehydrogenative coupling reactions
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Starting from arylboronic acids and ester (Z)-3-aminoacrylates, one-pot syntheses of diverse indole-3-carboxylic esters have been described through copper(ii)-catalyzed sequential Chan-Lam N-arylation and cross-dehydrogenative coupling (CDC) reactions. The initial Chan-Lam arylation can proceed in DMF at 100 °C for 24 h to give ester (Z)-3-(arylamino)acrylate intermediates in the presence of Cu(OAc)2/tri-tert-butylphosphine tetrafluoroborate, a catalytic amount of myristic acid as the additive, KMnO4 and KHCO3. Sequentially, these in situ arylated intermediates can undergo an intramolecular oxidative cross-dehydrogenative coupling process in mixed solvents (DMF/DMSO = 2 : 1) at 130 °C to give C3-functionalized multi-substituted indole derivatives. This journal is
- Bian, Yunyun,Chen, Chunxia,Chen, Xin,Mo, Baichuan,Peng, Jinsong,Sun, Peng
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p. 24830 - 24839
(2020/07/14)
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- Metal-Free Tandem Rearrangement/Lactonization: Access to 3,3-Disubstituted Benzofuran-2-(3H)-ones
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A novel metal-free synthesis of 3,3-disubstituted benzofuran-2-(3H)-ones through reacting α-aryl-α-diazoacetates with triarylboranes is presented. Initially, triarylboranes were successfully investigated in α-arylations of α-diazoacetates, however in the presence of a heteroatom in the ortho position, the boron enolate intermediate undergoes an intramolecular rearrangement to form a quaternary center. The intermediate cyclizes to afford valuable 3,3-disubstituted benzofuranones in good yields.
- Santi, Micol,Ould, Darren M. C.,Wenz, Jan,Soltani, Yashar,Melen, Rebecca L.,Wirth, Thomas
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supporting information
p. 7861 - 7865
(2019/04/25)
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- Synthesis of Substituted Indole-3-carboxylates by Iron(II)-Catalyzed Domino Isomerization of 3-Alkyl/aryl-4-aryl-5-methoxyisoxazoles
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The iron(II)-catalyzed domino isomerization of 3-alkyl/aryl-4-arylisoxazoles provides a selective access to a wide range of structurally diverse highly substituted indole-3-carboxylates. The operational simplicity, high atom efficiency, and the use of stable starting materials and an inexpensive and low-toxicity catalyst are some of the attractive features of this tandem double ring-opening-ring-closure strategy.
- Bodunov, Vladimir A.,Galenko, Ekaterina E.,Galenko, Alexey V.,Novikov, Mikhail S.,Khlebnikov, Alexander F.
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p. 2784 - 2798
(2018/06/08)
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- Copper-Catalyzed Synthesis of Multisubstituted Indoles through Tandem Ullmann-Type C-N Formation and Cross-dehydrogenative Coupling Reactions
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Multisubstituted indoles were synthesized via a one-pot tandem copper-catalyzed Ullmann-type C-N bond formation/intramolecular cross-dehydrogenative coupling process at 130 °C in DMSO. The methodology allows practical and modular assembly of indoles in go
- Li, Yue,Peng, Jinsong,Chen, Xin,Mo, Baichuan,Li, Xue,Sun, Peng,Chen, Chunxia
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p. 5288 - 5294
(2018/05/17)
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- Synthesis of 2,3-Disubstituted NH Indoles via Rhodium(III)-Catalyzed C-H Activation of Arylnitrones and Coupling with Diazo Compounds
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A rhodium-catalyzed intermolecular coupling between arylnitrones and diazo compounds by C-H activation/[4 + 1] annulation with a C(N2)-C(acyl) bond cleavage is reported, and 2,3-disubstituted NH indoles are directly synthesized in up to a 94% yield. A variety of functional groups are applicable to this reaction to give the corresponding products with high selectivity. Compared to other previously reported Rh(III)-catalyzed synthesis of homologous series, this method is simpler, more general, and more efficient.
- Guo, Xin,Han, Jianwei,Liu, Yafeng,Qin, Mingda,Zhang, Xueguo,Chen, Baohua
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p. 11505 - 11511
(2017/11/10)
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- Visible-Light-Induced Direct Photocatalytic Carboxylation of Indoles with CBr4/MeOH
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Photocatalysis enables the cascade reactions of indoles and CBr4 in MeOH through a C(sp2)-H functionalization/methanolysis sequence. The title reaction provides an efficient access to indole 2- and 3-carboxylates in a single operation (no preinstallation of protecting as well as directing groups was required) with good yields under mild reaction conditions. Shedding light on indole: The regioselective alkoxycarboxylation of indoles and heteroarenes using the CBr4/MeOH couple was accomplished through visible-light-induced photoredox catalysis. The described photocatalytic strategy features operational simplicity as well as high functional-group tolerance and represents a direct procedure to access indole carboxylates in generally moderate to good yields (see scheme).
- Yang, Qing-Qing,Marchini, Marianna,Xiao, Wen-Jing,Ceroni, Paola,Bandini, Marco
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supporting information
p. 18052 - 18056
(2015/12/24)
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- Efficient synthesis of useful heterocycles via transition metal-catalyzed cascade processes
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This paper reports our recent results from synthesis of some useful heterocycles, for example oxazolidinones, indoles, and quinoxalinones, by transition metal-catalyzed cascade processes. The scope and limitations of these procedures and the reaction mech
- Tanimori, Shinji,Inaba, Ushio,Kato, Yoshihiro,Ura, Haruna,Kashiwagi, Hiroaki,Nishimura, Takeshi,Kirihata, Mitsunori
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p. 2157 - 2164
(2014/06/24)
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- A catalyst-controlled selective synthesis of pyridines and pyrroles
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We have developed a dual reaction manifold that enables the selective synthesis of both pyridines and pyrroles from the common substrates α-diazo oxime ethers. The strong propensity of 1,3-dienyl nitrenes for 4π-electrocyclization to give pyrroles could be diverted to 6π-electrocyclization via a 1,6-hydride shift or prototropic isomerization, leading to the exclusive formation of pyridines by employing metal nitrene complexes derived from α-diazo oxime ethers under Rh(ii) catalysis. Furthermore, an orthogonal catalytic system has been identified that promotes the selective formation of 1H-pyrroles from the same substrates by redirecting the reactivity of vinyl 2H-azirine intermediates. This journal is the Partner Organisations 2014.
- Jiang, Yaojia,Park, Cheol-Min
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p. 2347 - 2351
(2014/05/20)
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- Regioselective synthesis of indoles via rhodium-catalyzed C-H activation directed by an in-situ generated redox-neutral group
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A regioselective synthesis of indoles from arylhydrazine hydrochlorides with alkynes and diethyl ketone catalyzed by a rhodium complex is described. A possible mechanism involving an in-situ generated oxidizing directing group -N-Ni'CR1R2 assisted ortho-C-H activation and reductive elimination are proposed. The catalytic reaction is highly compatible with a wide range of functional arylhydrazines and alkynes. The reaction proceeds under mild reaction conditions and is atom-step economical.
- Muralirajan, Krishnamoorthy,Cheng, Chien-Hong
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supporting information
p. 1571 - 1576
(2014/06/09)
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- Synthesis of diversely substituted indoloquinolinones via Pd(II)/Cu(II)-mediated oxidative C-C bond formation and I(III)-mediated C-N bond formation
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A series of indoloquinolinones bearing different aromatic substitutents were readily synthesized starting from an aryl amine, a methyl 3-oxo-3-phenylpropanoate derivative, and methoxylamine through a series of reactions of coupling/enamination, oxidative
- Zhang, Xiang,Zhang-Negrerie, Daisy,Deng, Jun,Du, Yunfei,Zhao, Kang
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p. 12750 - 12759
(2014/01/17)
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- A general synthesis of indole-3-carboxylic esters by palladium-catalyzed direct oxidative carbonylation of 2-alkynylaniline derivatives
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A general synthesis of indole-3-carboxylic esters by direct Pd-catalyzed oxidative carbonylation of readily available 2-alkynylaniline derivatives is reported. In particular, 2-alkynylanilines bearing an internal triple bond and a secondary amino group (1) were directly converted into indole-3-carboxylic esters 2 in fair to good yields (50-84%) when let to react with CO, O 2, and an alcohol in the presence of the PdI2/ KI catalytic system, under relatively mild conditions [100 °C and 20 atm (at 25 °C) of a 4:1 mixture CO/air]. On the other hand, under similar conditions, but in the presence of HC(OMe)3, 2-alkynylanilines bearing an internal triple bond and a primary amino group (7) afforded 1-(dimethoxymethyl) indole-3-carboxylic esters 9 through the intermediate formation of N-(dimethoxymethyl)-2-alkynylaniline derivatives II. Compounds 9 could be conveniently converted into Nunsubstituted indole-3-carboxylic esters 10 by a simple acidic treatment carried out in MeOH/H2O at 80 °C.
- Gabriele, Bartolo,Veltri, Lucia,Mancuso, Raffaella,Salerno, Giuseppe,Costa, Mirco
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p. 2549 - 2559
(2013/08/23)
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- Design and synthesis of indomethacin analogues that inhibit P-glycoprotein and/or multidrug resistant protein without Cox inhibitory activity
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We designed and synthesized conformationally restricted analogues and regioisomers of the nonsteroidal anti-inflammatory drug indomethacin. Evaluation of the inhibitory effects of these compounds on COX, P-glycoprotein, and multidrug resistance indicated that NSAIDS modulation of multidrug-resistant P-glycoprotein and multidrug-resistant protein-1 is not associated with COX-1 and COX-2 inhibitory activities.
- Arisawa, Mitsuhiro,Kasaya, Yayoi,Obata, Tohru,Sasaki, Takuma,Nakamura, Tomonori,Araki, Takuya,Yamamoto, Koujirou,Sasaki, Akito,Yamano, Akihito,Ito, Mika,Abe, Hiroshi,Ito, Yoshihiro,Shuto, Satoshi
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supporting information
p. 8152 - 8163
(2012/11/07)
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- A general synthesis of indole-3-carboxylic esters by palladium-catalyzed direct oxidative carbonylation of 2-alkynylaniline derivatives
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A general synthesis of indole-3-carboxylic esters by direct Pd-catalyzed oxidative carbonylation of readily available 2-alkynylaniline derivatives is reported. In particular, 2-alkynylanilines bearing an internal triple bond and a secondary amino group (1) were directly converted into indole-3-carboxylic esters 2 in fair to good yields (50-84%) when let to react with CO, O 2, and an alcohol in the presence of the PdI2/KI catalytic system, under relatively mild conditions [100 °C and 20 atm (at 25 °C) of a 4:1 mixture CO/air]. On the other hand, under similar conditions, but in the presence of HC(OMe)3, 2-alkynylanilines bearing an internal triple bond and a primary amino group (7) afforded 1-(dimethoxymethyl)indole-3- carboxylic esters 9 through the intermediate formation of N-(dimethoxymethyl)-2- alkynylaniline derivatives II. Compounds 9 could be conveniently converted into N-unsubstituted indole-3-carboxylic esters 10 by a simple acidic treatment carried out in MeOH/H2O at 80 °C.
- Gabriele, Bartolo,Veltri, Lucia,Mancuso, Raffaella,Salerno, Giuseppe,Costa, Mirco
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p. 2549 - 2559
(2012/06/01)
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- Cross-dehydrogenative coupling between enamino esters and ketones: Synthesis of tetrasubstituted pyrroles
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Tetrasubstituted pyrroles have been synthesized via the cross-dehydrogenative coupling between enamino esters and acetone. Silver carbonate proved to be an effective oxidant, and no transition metal catalyst is necessary.
- Zhao, Miao,Wang, Fen,Li, Xingwei
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p. 1412 - 1415
(2012/05/04)
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- Exploring the oxidative cyclization of substituted N-aryl enamines: Pd-catalyzed formation of indoles from anilines
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The direct Pd-catalyzed oxidative coupling of two C-H-bonds within N-aryl-enamines 1 allows the efficient formation of differently substituted indoles 2. In this cross-dehydrogenative coupling, many different functional groups are tolerated and the starting material N-aryl-enamines 1 can be easily prepared in one step from commercially available anilines. In addition, the whole sequence can also be run in a one-pot fashion. Optimization data, mechanistic insight, substrate scope, and applications are reported in this full paper. Copyright
- Neumann, Julia J.,Rakshit, Souvik,Droege, Thomas,Wuertz, Sebastian,Glorius, Frank
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supporting information; experimental part
p. 7298 - 7303
(2011/08/21)
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- Lewis acid catalyzed indole synthesis via intramolecular nucleophilic attack of phenyldiazoacetates to iminium ions
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(Chemical Equation Presented) Lewis acids catalyze the cyclization of methyl phenyldiazoacetates with an ortho-imino group, prepared from o-aminophenylacetic acid, to give 2,3-substituted indoles in quantitative yields.
- Zhou, Lei,Doyle, Michael P.
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supporting information; experimental part
p. 9222 - 9224
(2010/03/01)
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- Palladium-catalyzed synthesis of 3-indolecarboxylic acid derivatives
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Indoles having an ester functionality in the 3-position were prepared from 2-(2-nitrophenyl)propenoic acid derivatives via a palladium-catalyzed reductive N-heteroannulation using carbon monoxide as the ultimate reducing agent. The starting materials were
- Soederberg, Bjoern C. G.,Banini, Serge R.,Turner, Michael R.,Minter, Aaron R.,Arrington, Amanda K.
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p. 903 - 912
(2008/09/21)
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- A direct entry to the 1-methoxyindole skeleton and to the corresponding indoles by a novel rearrangement: General syntheses of substituted 1-methoxyindoles
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A short and efficient route to 1-methoxyindoles via a novel rearrangement is disclosed. This route involves only three steps from commercially available nitro compounds. The methodology is also generalized with a variety of examples to afford a series of
- Selvakumar,Reddy, B. Yadi,Azhagan, A. Malar,Khera, Manoj Kumar,Babu, J. Moses,Iqbal, Javed
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p. 7065 - 7069
(2007/10/03)
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- Deprotection of N-sulfonyl nitrogen-heteroaromatics with tetrabutylammonium fluoride
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The deprotection of N-methylsulfonyl, N-(p-toluenesufonyl), and N-phenylsulfonyl nitrogen-heteroaromatic compounds proceeds easily in excellent yields by refluxing with tetrabutylammonium fluoride (TBAF) in THF.
- Yasuhara, Akito,Sakamoto, Takao
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p. 595 - 596
(2007/10/03)
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- Condensed heteroaromatic ring systems. XXIV. Palladium-catalyzed cyclization of 2-substituted phenylacetylenes in the presence of carbon monoxide
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The palladium-catalyzed reaction of 2-alkynylanilines and 2-alkynylphenols in the presence of carbon monoxide and methanol under basic conditions gave the sequential cyclization/carbonylation products, methyl 2-substituted indole and benzo[b]furan-3-carbo
- Kondo, Yoshinori,Shiga, Futoshi,Murata, Naoko,Sakamoto, Takao,Yamanaka, Hiroshi
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p. 11803 - 11812
(2007/10/02)
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- Prototropic Generation of Dipoles. A New Synthesis of Indole-3-carboxylic Acids
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Imines of (2-aminophenyl)acetic acid give 2-substituted indole-3-carboxylic acids under mild conditions; the cyclisation is thought to involve a 1,5-dipole and initially to give the corresponding indolines.
- Grigg, Ronald,Gunaratne, H. Q. Nimal
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p. 661 - 662
(2007/10/02)
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- Photochemistry of Dimethyl Quinoline-3,4-dicarboxylate N-Oxides
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The photochemical rearrangement of 2-methyl and 2-aryl substituted dimethyl quinoline-3,4-dicarboxylate N-oxides has been studied.In methanol or methanol/chloroform solutions the major product was the 1-methyl- or 1-aryl-quinolin-2-(1H)-one in which the substituent at C2 has migrated to nitrogen.The yield of these products was increased in a dark reaction subsequent to the irradiation.In acetonitrile solutions the initial major product was the corresponding 3,1-benzoxazepine; subsequent reactions yielded inter alia indole derivatives.
- Irvine, Robert W.,Summers, John C.,Taylor, Walter C.
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p. 1419 - 1430
(2007/10/02)
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- Studies on the N-Oxides of ?-Deficient N-Heteroaromatics. XXXVI. Photochemical and Thermal Michael Reactions of Alcohols with Methyl 2-Phenyl-3,1-benzoxazepine-5-carboxylate and Its Derivatives
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Irradiation (>/=300 nm) of methyl 2-phenyl-3,1-benzoxazepine-5-carboxylate in an alcohol afforded the Z-isomer of methyl 3-alkoxy-2-(2-benzamidophenyl)-acrylate as the major product.In contrast, thermal reaction of the oxazepine with a primary alcohol in
- Kaneko, Chikara,Fujii, Harue,Kawai, Shinji,Hashiba, Kazuhiko,Karasawa, Yoshio,et al.
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