- Ru(II)–NNO pincer-type complexes catalysed E-olefination of alkyl-substituted quinolines/pyrazines utilizing primary alcohols
-
An efficient and selective E-olefination of alkyl-substituted quinolines and pyrazines through acceptorless dehydrogenative coupling of alcohols catalysed by Ru(II)–N^N^O pincer-type complexes encompassing carbonyl and triphenylarsines as co-ligands is de
- Balamurugan, Gunasekaran,Malecki, Jan Grzegorz,Ramesh, Rengan,Tamilthendral, Veerappan
-
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- Nickel(II)-Catalyzed Selective (E)-Olefination of Methyl Heteroarenes Using Benzyl Alcohols via Acceptorless Dehydrogenative Coupling Reaction
-
An efficient catalytic protocol for the synthesis of selective (E)-olefins by the newly synthesized nickel complexes via greener acceptorless dehydrogenative coupling methodology is presented. Two nickel(II) N, S chelating complexes were structurally characterized with the aid of spectral and single crystal X-ray diffraction methods. Olefination of 2-methylheteroarenes with benzyl alcohols via acceptorless dehydrogenative coupling is achieved by inexpensive nickel(II) catalysts. The present olefination protocol is simple and furnishes the desired 2-alkenylheteroarenes in 35 h and yields in the range of 40–93 %. The dehydrogenative coupling reaction proceeds via the generation of an aldehyde intermediate and produces water and hydrogen as sole by-products. The wide substrate scope of this catalytic reaction covered the synthesis of drug intermediates.
- Balamurugan, Gunasekaran,Ramesh, Rengan
-
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- Deaminative Olefination of Methyl N-Heteroarenes by an Amine Oxidase Inspired Catalyst
-
We explored the bioinspired o-quinone cofactor catalyzed aerobic primary amine dehydrogenation for a cascade olefination reaction with nine different methyl N-heteroarenes, including pyrimidines, pyrazines, pyridines, quinolines, quinoxolines, benzimidazoles, benzoxazoles, benzthiazoles, and triazines. An o-quinone catalyst phd (1,10-phenanthroline-5,6-dione) combined with a Br?nsted acid catalyzed the reaction. N-Heteroaryl stilbenoids were synthesized in high yields and (E)-selectivities under mild conditions using oxygen (1 atm) as the sole oxidant without needing transition-metal salt, ligand, stoichiometric base, or oxidant.
- Thorve, Pradip Ramdas,Maji, Biplab
-
supporting information
p. 542 - 547
(2021/01/26)
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- NH4I-mediated sp3 C-H cross-dehydrogenative coupling of benzylamines with 2-methylquinoline for the synthesis of E-2-styrylquinolines
-
Without any metal catalyst, a simple and efficient method for the synthesis of E-2-styrylquinolines through sp3 C-H cross-dehydrogenative coupling of benzylamines with 2-methylquinolines mediated by NH4I under air is successfully developed. The oxidative olefination proceeded through deamination and sp3 C–H bond activation. A plausible mechanism is proposed for the construction of E-2-styrylquinolines.
- Huang, Bin,Li, Xue,Liao, WeiBo,Wang, JiangWei,Zhang, YuanYuan
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p. 903 - 910
(2021/07/17)
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- Method for alkenylation of methyl heterocyclic compound
-
The invention discloses a method for alkenylation of methyl heterocyclic compound, which is a green method for synthesizing an alkenyl heterocyclic compound by carrying out alkenylation reaction on methyl under the condition that the methyl heterocyclic compound and alcohol do not need to participate in a transition metal catalyst. According to the method, alcohol which is cheap, easy to obtain, wide in source, stable and low in toxicity is used as an alkenylation reagent, no transition metal catalyst or ligand is needed, air can be directly used as a convenient, mild and efficient oxidizing agent under the action of common water-soluble inorganic base, and the method is suitable for industrial production. The alkenyl heterocyclic compound is directly synthesized by carrying out a Cenylation reaction with a methyl heterocyclic compound through processes such as oxidative condensation and the like. The method has the advantages of simple reaction conditions, no need of inert gas protection, low requirements on equipment, easiness in operation, water as a byproduct, easiness in removal of water-soluble inorganic base, no metal residue in the product, easiness in purification, suitability for heterocyclic systems such as quinoline, quinoxaline, pyridine, benzothiazole and the like, and wide application range, thereby having certain research significance and potential application prospect.
- -
-
Paragraph 0099-0102
(2021/02/10)
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- Metal-Free Synthesis of Alkenylazaarenes and 2-Aminoquinolines through Base-Mediated Aerobic Oxidative Dehydrogenation of Benzyl Alcohols
-
A metal-free, base-mediated, and atom-efficient oxidative dehydrogenative coupling of substituted phenylmethanols (benzyl alcohols) with methyl azaarenes or phenylacetonitriles to afford substituted alkenylazaarenes or 2-aminoquinolines, respectively is described. CsOH.H2O was discovered to be the base of choice for obtaining optimal yields of the title compounds, although the reaction could proceed with KOH as well. The protocol that works efficiently in the presence of air is amenable over broad range of substrates.
- Batra, Sanjay,Dahatonde, Dipak J.,Ghosh, Aritra
-
p. 2746 - 2751
(2021/06/25)
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- Waste-minimized synthesis of C2 functionalized quinolines exploiting iron-catalysed C-H activation
-
Herein we present an efficient and regioselective iron-catalyzed methodology for the external oxidant-free functionalization of quinoline-N-oxides. The protocol, based on the use of inexpensive and easily accessible FeSO4, showed broad applicability to a wide range of substrates. An additional green feature of this synthetic methodology is H2O being the only by-product. Experimental and computational investigations provide support to a mechanism based on a facile C-H activation event. The green efficiency of the process has also been carefully assessed using: (i) metrics related to the synthetic process (AE, Yield, 1/SF, MRP and RME); (ii) safety/hazard metrics (SHZI and SHI); and (iii) metrics related to the metal used as the catalyst (Abundance, OEL and ADP). In addition to the many advantages of this protocol related to the green iron catalyst used and the safety/hazard features of the process, an E-factor value of ca. 0.92 (84 to >99% reduction compared to known protocols) evidently confirms the sustainable efficiency of the procedure presented. Practical utility has also been demonstrated by performing the reaction efficiently on a multi-gram scale. This journal is
- Ferlin, Francesco,Zangarelli, Agnese,Lilli, Simone,Santoro, Stefano,Vaccaro, Luigi
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p. 490 - 495
(2021/01/28)
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- Malononitrile-activated synthesis and anti-cholinesterase activity of styrylquinoxalin-2(1: H)-ones
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Herein, we report a base-free malononitrile activated condensation of 3-methylquinoxaline-2(1H)-one (3MQ) 1 with aryl aldehydes 3a-3ad for synthesis of styrylquinoxalin-2(1H)-ones (SQs) 4a-4ad with excellent yields. In this reaction, malononitrile activates the aldehyde via Knoevenagel condensation towards reaction with 3MQ 1 and gets liberated during the course of reaction to yield the desired SQs 4a-4ad. The SQs were evaluated for in vitro cholinesterase inhibition and 4n was found to display a mixed type of inhibition of AChE, which was supported by molecular modelling studies. This study has led to the discovery of a new chemotype for cholinesterase inhibition which might be useful in finding a remedy for Alzheimer's disease.
- Bharate, Sandip B.,Kapoor, Kamal K.,Mahajan, Sheena,Nuthakki, Vijay K.,Slathia, Nancy
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p. 15966 - 15975
(2020/05/13)
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- NaCl as Catalyst and Water as Solvent: Highly E-Selective Olefination of Methyl Substituted N-Heteroarenes with Benzyl Amines and Alcohols
-
Oxidative coupling of benzylamines and alcohols with methyl substituted N-heteroarenes such as quinolines and quinoxalines has been achieved using chloride, a sea abundant anion as the catalyst for practical synthesis of a wide range of E-disubstituted olefins in aqueous medium. Detailed mechanistic studies and control experiments were carried out to deduce the reaction mechanism which indicated that in situ formed ClO2- is the active form of the catalyst. We have successfully carried out a 1 g scale reaction using this methodology, and five pharmaceutically relevant conjugated olefins were also synthesized by this method in moderate to good yields.
- Hazra, Susanta,Tiwari, Vikas,Verma, Ashutosh,Dolui, Pritam,Elias, Anil J.
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supporting information
p. 5496 - 5501
(2020/07/14)
-
- Aryl-Nickel-Catalyzed Benzylic Dehydrogenation of Electron-Deficient Heteroarenes
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This manuscript describes the first practical benzylic dehydrogenation of electron-deficient heteroarenes, including pyridines, pyrazines, pyrimidines, pyridazines, and triazines. This transformation allows for the efficient benzylic oxidation of heteroarenes to afford heterocyclic styrenes by the action of nickel catalysis paired with an unconventional bromothiophene oxidant.
- Zhang, Pengpeng,Huang, David,Newhouse, Timothy R.
-
supporting information
p. 1757 - 1762
(2020/02/04)
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- MnO2 mediated sequential oxidation/olefination of alkyl-substituted heteroarenes with alcohols
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A practical and efficient ligand-free MnO2 mediated sequential oxidation and olefination has been developed for the facile synthesis of a broad range of unsaturated N-heteroazaarenes from simple alkyl-substituted heteroarenes and alcohols. The procedure tolerates a series of functional groups, such as methoxyl, chloro, bromo, iodo, vinyl, phenolic and hetero groups, providing the olefination products in moderate to good yields.The protocol could be conducted at mild conditions and used environmentally friendly air as the clear oxidant.
- Zhang, Chunyan,Li, Zehua,Fang, Yanchen,Jiang, Shaohua,Wang, Maorong,Zhang, Guoying
-
supporting information
(2020/02/15)
-
- Preparation method of trans-disubstituted olefin
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The invention relates to the technical field of organic chemical synthesis, and in particular, relates to a preparation method of trans-disubstituted olefin. According to the preparation method, primary alcohol and methyl azacycle are taken as raw materials, transition metal salt, nitric oxide and alkali are taken as catalysts, an organic solution is taken as a reaction medium, and reaction is carried out in an oxygen atmosphere. According to the preparation method, a reaction by-product is only water, the environment is not polluted, the required transition metal catalyst is cheap and easy toobtain, the reaction does not need high temperature, and the reaction cost and the requirements on reaction conditions can be reduced.
- -
-
Paragraph 0030-0037; 0166-0228
(2020/02/27)
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- Iron/TEMPO-catalyzed direct aerobic oxidative coupling of methyl-mubstituted N-heteroazaarenes with alcohols
-
A novel direct oxidative coupling of methyl-substituted N-heteroazaarenes with alcohols has been developed to construct olefins under mild condition. The reaction is catalyzed by Fe(NO3)3·9H2O/TEMPO with oxygen as terminal oxidant. A variety of E-disubstituted olefins bearing diverse functional groups could be obtained selectively in moderate to excellent yields. The reaction is environmentally friendly and ligand-free.
- Zhang, Zhiguang,Ma, Yantao,Dai, Siwei,Li, Ling,Zhang, Yong,Li, Hao
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supporting information
(2020/04/21)
-
- A heterogeneous and recoverable palladium catalyst to access the regioselective C-H alkenylation of quinoline: N -oxides
-
Herein, we disclose the first C-2-selective C-H alkenylation of quinoline N-oxides catalyzed using a heterogeneous palladium catalyst. The protocol does not require the use of an external oxidant and it is applicable to an ample substrate scope always showing excellent site selectivity. This process is made accessible by the use of a specific 1,2,3-triazolium-tagged heterogeneous polymeric catalytic system. The catalyst can be efficiently recovered and reused with no decrease of its catalytic performance and hot filtration and mercury poisoning tests suggest that its mechanism of action is operatively heterogeneous. In addition, mechanistic studies revealed that C-H activation reaction pathways are operative, setting the stage for the direct synthesis of 2-functionalized quinolines using N-oxide functionality as both a directing group and an oxidant.
- Chen, Shaomin,Ferlin, Francesco,Gu, Yanlong,Piermatti, Oriana,Sciosci, Daniele,Vaccaro, Luigi,Valentini, Federica
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p. 6560 - 6566
(2020/11/09)
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- Direct Alkenylation of 2-Methylquinolines with Aldehydes through Synergistic Catalysis of 1,3-Dimethylbarbituric Acid and HOAc
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An efficient and practical direct alkenylation of 2-methylquinolines with aldehydes has been achieved through a novel synergistic organocatalysis. The HOAc- activated 2-methylquiolines undergo a Michael addition to 1,3-dimethylbarbituric acid-activated aldehydes, followed by a retro-Michael addition to release 1,3-dimethylbarbituric acid and the target products. The transformation produced various 2-alkenylquinolines with good to excellent yields and featured mild reaction conditions, atom- and step-economy, good functional group tolerance, and operational simplicity. (Figure presented.).
- Liang, En,Wang, Junqi,Wu, Yinrong,Huang, Liangbin,Yao, Xingang,Tang, Xiaodong
-
supporting information
p. 3619 - 3623
(2019/07/10)
-
- Green synthesis method of alkenyl azaarene compounds
-
The invention discloses a green synthesis method of alkenyl azaarene compounds. The process of the method is as follows: 2-methyl quinoline derivatives and aldehyde compounds are used as reaction rawmaterials, acids and active methylene compounds are used
- -
-
Paragraph 0032-0034
(2019/10/01)
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- Microwave-assisted, rapid synthesis of 2-vinylquinolines and evaluation of their antimalarial activity
-
A rapid and efficient synthesis of 2-vinylquinolines via trifluoromethanesulfonamide-mediated olefination of 2-methylquinoline and aldehyde under microwave irradiation is reported. Biological evaluation of these scaffolds demonstrates that 2-vinylquinolines 3x-3z possess excellent antimalarial activities against chloroquine-resistant Dd2 strain of Plasmodium falciparum (IC50 100 nM).
- Huang, Guang,Solano, Claribel Murillo,Su, Yuxin,Ezzat, Nameer,Matsui, Shino,Huang, Liuyu,Chakrabarti, Debopam,Yuan, Yu
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supporting information
p. 1736 - 1740
(2019/06/05)
-
- Copper-Catalyzed Regio- and Enantioselective Addition of Silicon Grignard Reagents to Alkenes Activated by Azaaryl Groups
-
A new application of silicon Grignard reagents in C(sp3)?Si bond formation is reported. With the aid of BF3?OEt2, these silicon nucleophiles add across alkenes activated by various azaaryl groups under copper catalysis. An enantioselective version employing benzoxazole-activated alkenes as substrates and a CuI-josiphos complex as catalyst has been developed, forming the C(sp3)?Si bond with good to high enantiomeric ratios (up to 97:3). The method expands the toolbox for “conjugate addition” type C(sp3)?Si bond formation.
- Mao, Wenbin,Xue, Weichao,Irran, Elisabeth,Oestreich, Martin
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supporting information
p. 10723 - 10726
(2019/07/04)
-
- 2-Styrylquinoline-based two-photon AIEgens for dual monitoring of pH and viscosity in living cells
-
A new class of aggregation-induced emission (AIE) fluorophores HAPHs with excellent two-photon properties is developed from styrylquinoline. Among them, the probe HAPH-1 exhibits good sensitivity towards pH and viscosity and has been successfully used for
- Dou, Yandong,Liu, Jiang,Zhang, Fangfang,Cai, Chunhui,Zhu, Qing,Kenry
-
supporting information
p. 7771 - 7775
(2019/12/26)
-
- Cascade Knoevenagel and aza-Wittig reactions for the synthesis of substituted quinolines and quinolin-4-ols
-
A [4 + 2] annulation involving cascade Knoevenagel, aza-Wittig and dehydrofluorination reactions is developed for the synthesis of substituted quinolin-4-ols including analogs bearing CF2H, CF3, and C2F5 groups. This simple and highly efficient method is also applicable for the synthesis of substituted quinolines. A number of reported biologically active compounds can be readily prepared by this one-pot synthesis. Green chemistry metrics analysis of the new reaction processes provided favorable results.
- Zhang, Xiaofeng,Ma, Xiaoming,Qiu, Weiqi,Evans, Jason,Zhang, Wei
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p. 349 - 354
(2019/01/28)
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- Nickel-catalysed direct α-olefination of alkyl substituted N-heteroarenes with alcohols
-
Catalytic α-olefination of alkylheteroarenes with primary alcohols via dehydrogenative coupling is presented. A simple nickel catalyst system stabilised by readily available nitrogen ligands enables a series of interesting E-configured vinylarenes (confirmed by X-ray crystal-structure analysis) to be synthesised in good to excellent yields with olefin/alkane selectivity of >20:1. Hydrogen and water are generated as byproducts and quantitative determination of H2 was performed.
- Das, Jagadish,Vellakkaran, Mari,Banerjee, Debasis
-
supporting information
p. 7530 - 7533
(2019/07/04)
-
- Nickel-Catalyzed Direct Alkenylation of Methyl Heteroarenes with Primary Alcohols
-
An efficient nickel-catalyzed acceptorless dehydrogenative coupling of methyl-substituted heteroarenes with primary alcohols is achieved using an in situ generated complex of inexpensive NiBr2 and readily available 8-aminoquinoline picolinic amide ligand. The protocol is operationally simple and scalable and furnishes a series of high-value 2-alkenylheteroarenes in good yields (up to 88percent) with exclusive E-selectivity. The reaction proceeds with the release of water and molecular hydrogen, which was analyzed through gas chromatography to validate the reaction mechanism. ?
- Baidya, Mahiuddin,Ramakrishna, Isai,Ramalingam, Bose Muthu
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p. 9819 - 9825
(2019/08/26)
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- Iron-Catalyzed Coupling of Methyl N-Heteroarenes with Primary Alcohols: Direct Access to E-Selective Olefins
-
An efficient Fe-catalyzed system is reported for direct α-olefination of methyl-substituted N-heteroarenes with primary alcohols. The catalytic dehydrogenative coupling enables a series of functionalized E-olefinated N-heteroaromatics with excellent selectivity (>99%). Initial mechanistic studies including deuterium-labeling experiments provide evidence for the participation of the benzylic C-H/D bond of alcohols.
- Das, Jagadish,Vellakkaran, Mari,Sk, Motahar,Banerjee, Debasis
-
supporting information
p. 7514 - 7518
(2019/10/02)
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- Manganese-Catalyzed Dehydrogenative Alkylation or α-Olefination of Alkyl-Substituted N-Heteroarenes with Alcohols
-
Catalysis with earth-abundant transition metals is an option to help save our rare noble-metal resources and is especially interesting when novel reactivity or selectivity patterns are observed. We report here on a novel reaction, namely the dehydrogenative alkylation or α-olefination of alkyl-substituted N-heteroarenes with alcohols. Manganese complexes developed in our laboratory catalyze the reaction with high efficiency whereas iron and cobalt complexes stabilized by the same ligands are essentially inactive. Hydrogen is liberated during the reaction, and bromine and iodine functional groups as well as olefins are tolerated. A variety of alkyl-substituted N-heteroarenes can be functionalized, and benzylic and aliphatic alcohols undergo the reaction.
- Zhang, Guoying,Irrgang, Torsten,Dietel, Thomas,Kallmeier, Fabian,Kempe, Rhett
-
supporting information
p. 9131 - 9135
(2018/06/04)
-
- Synthesis of (E)-2-Alkenylazaarenes via Dehydrogenative Coupling of (Hetero)aryl-fused 2-Alkylcyclic Amines and Aldehydes with a Cobalt Nanocatalyst
-
To date, the synthesis of (E)-2-alkenylazaarenes via the condensation of 2-methyl N-heteroarenes with aldehydes or their equivalents has been well demonstrated. However, the direct formation of such a class of useful compounds from extensively distributed 2-alkylcyclic amine motifs remains an unresolved goal. Herein, by employing the nitrogen-silica-doped carbon (Vulcan XC-72R) as the support, we have developed a low-loading cobalt nanocatalyst (Co/N-Si-C). The combination of such a catalyst with p-nitrobenzoic acid and molecular O2 exhibits excellent catalytic performance towards the dehydrogenative coupling of (hetero)aryl-fused 2-alkylcyclic amines with aldehydes to afford the (E)-2-alkenylazaarenes. In the reaction, effective capture of the partially dehydrogenated cyclic amine motifs appears to be the key strategy to address the issue of the chemoselectivity. The developed catalytic transformation proceeds with the merits of broad substrate scope, good functional group tolerance, high atom-efficiency, use of an earth-abundant and reusable cobalt catalyst and molecular O2 as a green oxidant, which offers an important basis for the direct conversion of inert cyclic amine units into the functional frameworks.
- Zhou, Changjian,Tan, Zhenda,Jiang, Huanfeng,Zhang, Min
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p. 2887 - 2892
(2018/05/03)
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- A trans-substituted olefin preparation method (by machine translation)
-
This invention relates to a trans-substituted olefin preparation method, which belongs to the technical field of organic chemical synthesis. The method adopts the simple alcohol and methyl nitrogen-containing heterocyclic as the starting material, by transition metal-catalyzed alkene base reaction, to obtain trans-substituted olefin compound. The reaction raw material, catalyst and additives is cheap, simple synthesis technology, greatly reduces the cost of synthesizing; mild reaction conditions, high yield, easy industrialization; the reaction of raw materials and catalyst cleaning toxic, small pollution to the environment. The trans-substituted olefin compound and its derivatives as an important fine chemicals, in the medical, agricultural chemicals, perfume and photoelectric and other industries have wide application. (by machine translation)
- -
-
Paragraph 0112; 0113; 0115; 0016
(2018/07/30)
-
- Manganese-Catalyzed Direct Olefination of Methyl-Substituted Heteroarenes with Primary Alcohols
-
Herein, we present the first catalytic direct olefination of methyl-substituted heteroarenes with primary alcohols through an acceptorless dehydrogenative coupling. The reaction is catalyzed by a complex of the earth-abundant transition metal manganese that is stabilized by a bench-stable NNN pincer ligand derived from 2-hydrazinylpyridine. The reaction is environmentally benign, producing only hydrogen and water as byproducts. A large number of E-disubstituted olefins were selectively obtained with high efficiency.
- Barman, Milan K.,Waiba, Satyadeep,Maji, Biplab
-
supporting information
p. 9126 - 9130
(2018/07/25)
-
- Oxidant-Controlled C-sp2/sp3-H Cross-Dehydrogenative Coupling of N-Heterocycles with Benzylamines
-
Oxidant controlled ionic liquid mediated cross-dehydrogenative coupling (CDC) of benzylamines with N-heterocycles having sp2 or sp3 carbon resulted in the formation of C-benzoylated or alkenylated products. Benzoylation of N-heterocycles occurs via (NH4)2S2O8 catalyzed benzoyl radical formation. An oxidative alkenylation of N-heterocycles having C-sp3 carbon (2-methylaza-arenes) occurs via deamination of benzylamine followed by C-sp3-H bond activation in high stereoselectivity. Both benzoylation and alkenylation protocols are metal-free, green, simple, efficient, and tolerate a wide variety of functional groups.
- Sharma, Rohit,Abdullaha, Mohd,Bharate, Sandip B.
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p. 9786 - 9793
(2017/09/23)
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- Facile synthesis of 2-alkenylazaarenes via dehydrative coupling of 2-methylazaarenes with aldehydes ‘on water’
-
A catalyst-free dehydrative coupling of 2-methylazaarenes with aldehydes ‘on water’ has been developed for efficient synthesis of (E)-2-alkenylazaarenes. The challenging addition/dehydration of aliphatic aldehyde was successfully implemented using water as a solvent. A variety of 2-methylazaarenes, aromatic and aliphatic aldehydes were well tolerated.
- Fu, Shiheng,Wang, Liang,Dong, Haoxun,Yu, Junqiang,Xu, Lubin,Xiao, Jian
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supporting information
p. 4533 - 4536
(2016/09/23)
-
- Direct alkenylation of alkylazaarenes with aldehydes through C(sp3)-H functionalization under catalytic InCl3 activation
-
Under the influence of InCl3 as a Lewis acid catalyst, a methodology on the C(sp3)-H functionalization of alkylazaarenes has been demonstrated through the activation of benzylic C-H bonds towards their addition reaction with the appropriate electrophiles. This methodology was chiefly applied in the direct alkenylation of primary and secondary benzylic C-H bonds of alkylazaarenes with aldehydes. A variety of alkenyl products were afforded in generally good yields including the starting alkenyl intermediate used in the synthesis of montelukast and other related molecules.
- Jamal, Zaini,Teo, Yong-Chua,Lim, Gina Shiyun
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p. 2132 - 2138
(2016/04/19)
-
- Direct alkenylation of 2-substituted azaarenes with carbonyls via C-H bond activation using iron-based metal-organic framework Fe3O(BPDC)3 as an efficient heterogeneous catalyst
-
A porous crystalline metal-organic framework Fe3O(BPDC)3 was synthesized from the reaction of biphenyl-4,4′-dicarboxylic acid and iron(III) chloride hexahydrate by a solvothermal method in the presence of acetic acid, and was characterized by using a variety of different techniques. The Fe3O(BPDC)3 could be used as an efficient heterogeneous catalyst in the synthesis of 2-alkenylazaarenes using the direct alkenylation of 2-substituted azaarenes with carbonyls via C-H bond activation. The presence of acetic acid as a co-catalyst accelerated the transformation significantly. The Fe3O(BPDC)3 exhibited better performance in this transformation then other MOFs such as Fe3O(BDC)3, Cu2(OBA)2(BPY), Cu2(BDC)2(DABCO), Ni2(BDC)2(DABCO), Zn-MOF-74, and Cu2(NDC)2(DABCO). The Fe3O(BPDC)3 also exhibited higher catalytic activity than that of several homogeneous catalysts such as FeCl2, FeCl3, CuCl2, Zn(OAc)2, Zn(NO3)2, and Ni(OAc)2. The Fe3O(BPDC)3 catalyst could be recovered and reused several times in the synthesis of 2-alkenylazaarenes without a significant degradation in catalytic activity. To the best of our knowledge, 2-alkenylazaarenes was not previously synthesized via the direct alkenylation of 2-substituted azaarenes with carbonyls using heterogeneous catalysts.
- Dang, Hang T.,Lieu, Thien N.,Truong, Thanh,Phan, Nam T.S.
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p. 237 - 245
(2016/05/19)
-
- Lanthanum Pentafluorobenzoate-Catalyzed Aerobic Oxidative Olefination of Benzylamines with 2-Methylquinoline through Deamination and C-H Bond Functionalization
-
An efficient direct aerobic oxidative olefination of the methyl groups of 2-methylquinolines with benzylamines in the presence of a rare-earth-metal Lewis acid catalyst to give 2-styrylquinolines was successfully developed. Preliminary mechanistic studies revealed that the oxidative olefination reaction proceeds through a Lewis acid-catalyzed 2-methylquinoline-aldehyde condensation and an amine-aldehyde condensation.
- Mao, Dan,Zhu, Xiaoyan,Hong, Gang,Wu, Shengying,Wang, Limin
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supporting information
p. 2481 - 2484
(2016/10/21)
-
- Synthesis of 2-Alkenylquinoline by Reductive Olefination of Quinoline N-Oxide under Metal-Free Conditions
-
Synthesis of 2-alkenylquinoline by reductive olefination of quinoline N-oxide under metal-free conditions is disclosed. Practically, the reaction could be performed with quinoline as starting material via a one-pot, two-step process. A possible mechanism is proposed that involves a sequential 1,3-dipolar cycloaddition and acid-assisted ring opening followed by a dehydration process.
- Xia, Hong,Liu, Yuanhong,Zhao, Peng,Gou, Shaohua,Wang, Jun
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p. 1796 - 1799
(2016/05/19)
-
- C2-Alkenylation of N-heteroaromatic compounds: Via Br?nsted acid catalysis
-
Substituted heteroaromatic compounds, especially those based on pyridine, hold a privileged position within drug discovery and medicinal chemistry. However, functionalisation of the C2 position of 6-membered heteroarenes is challenging because of (a) the difficulties of installing a halogen at this site and (b) the instability of C2 heteroaryl-metal reagents. Here we show that C2-alkenylated heteroaromatics can be accessed by simple Br?nsted acid catalysed union of diverse heteroarene N-oxides with alkenes. The approach is notable because (a) it is operationally simple, (b) the Br?nsted acid catalyst is cheap, non-toxic and sustainable, (c) the N-oxide activator disappears during the reaction, and (d) water is the sole stoichiometric byproduct of the process. The new protocol offers orthogonal functional group tolerance to metal-catalysed methods and can be integrated easily into synthetic sequences to provide polyfunctionalised targets. In broader terms, this study demonstrates how classical organic reactivity can still be used to provide solutions to contemporary synthetic challenges that might otherwise be approached using transition metal catalysis.
- Crisenza, Giacomo E. M.,Dauncey, Elizabeth M.,Bower, John F.
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p. 5820 - 5825
(2016/07/06)
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- C(sp3)-H functionalization of methyl azaarenes: a calcium-catalyzed facile synthesis of (E)-2-styryl azaarenes and 2-aryl-1,3-bisazaarenes
-
Alkaline earth (Ca2+) catalyzed sp3 C-H functionalization of methyl azaarenes for the synthesis of biologically important (E)-2-styryl azaarenes, 2-aryl-1,3-bisazaarenes and 3,3-bisazaarenyl indolinones has been described. Initially methyl azaarenes react with aryl aldehydes to give β-hydroxy derivatives, which undergo Ca(II) catalyzed thermodynamic elimination to give the styryl azaarenes in a single step. Similarly it may undergo SN1 reaction to give 2-aryl-1,3-bisazaarenes and 3,3-bisazaarenyl indolinones (if isatin used as the electrophile). This green synthetic methodology enjoys the simple reaction procedures, solvent free conditions, step economy, substrate diversity and high yields of the products in short time.
- Yaragorla, Srinivasarao,Singh, Garima,Dada, Ravikrishna
-
supporting information
p. 5924 - 5929
(2015/11/02)
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- Regioselective Metal-Free Cross-Coupling of Quinoline N -Oxides with Boronic Acids
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A novel and operationally simple one-step C-H bond functionalization of quinoline N-oxides to 2-substituted quinolines was developed. This approach enables the regioselective functionalization under external oxidant- and metal-free conditions. The developed transformation represents the first application of the Petasis reaction in functionalization of heterocycles.
- Bering, Luis,Antonchick, Andrey P.
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p. 3134 - 3137
(2015/06/30)
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- Iron-catalyzed C(sp3)-H functionalization of methyl azaarenes: A green approach to azaarene-substituted α- Or β-hydroxy carboxylic derivatives and 2-alkenylazaarenes
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Bioactive azaarene-substituted lactic acids, β-hydroxy esters, 3-hydroxy-2H-indol-2-ones, and 2-alkenylazaarenes were prepared in moderate-to-excellent yields via C(sp3)-H functionalization of methyl azaarenes with carbonyl compounds in the presence of iron(ii) acetate as an inexpensive, nontoxic, efficient catalyst. The application of this atom-, step-economic, and environmentally friendly method was demonstrated by a gram-scale synthesis of 3-[(E)-2-(7-chloroquinolin-2-yl)vinyl]benzaldehyde, a key intermediate of leukotriene receptor antagonist (Montelukast).
- Pi, Danwei,Jiang, Kun,Zhou, Haifeng,Sui, Yuebo,Uozumi, Yasuhiro,Zou, Kun
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p. 57875 - 57884
(2015/01/08)
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- Cobalt-catalyzed direct alkenylation of 2-methylquinolines with aldehydes via C(sp3)-H functionalization in water
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The direct C(sp3)-H alkenylation of 2-methylquinolines with aldehydes as a simple methodology to afford 2-alkenylated quinolines is reported. In the presence of catalytic CoCl2 in water, the economically and ecologically sound transformation is proposed to proceed via the direct benzylic addition to the aldehyde followed by an elimination step to provide 2-alkenylated quinolines in good to excellent yield of up to 95%. Georg Thieme Verlag Stuttgart New York.
- Jamal, Zaini,Teo, Yong-Chua
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supporting information
p. 2049 - 2053
(2014/11/08)
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- Catalyst-free synthesis of (E)-2-alkenylquinoline derivatives via C(sp3)-H functionalization of 2-methylquinolines
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This Letter described a facile approach to synthesize (E)-2-alkenylquinoline derivatives via C(sp3)-H functionalization of 2-methylquinolines under catalyst-free conditions. A variety of electronically and sterically diverse 2-methyl quinoline and aromatic aldehydes were well tolerated.
- Xu, Lubin,Shao, Zhuzhou,Wang, Liang,Zhao, Huaili,Xiao, Jian
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supporting information
p. 6856 - 6860
(2015/01/09)
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- Lewis-acid-catalyzed benzylic reactions of 2-methylazaarenes with aldehydes
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Lewis-acid-catalyzed benzylic reactions of 2-methylazaarenes with aldehydes have been investigated. Series of azaarene derivatives were afforded by this reaction. 2-(Pyridin-2-yl)ethanols with common substituents were formed through the LiNTf2-promoted aldol reaction for the first time. 2-Alkenylpyridines, exclusively in the form of the E isomers, were synthesized in the presence of LiNTf2 cooperated with H2NTf. In the presence of La(Pfb)3 as catalysis, 2-alkenylquinolines were obtained in high yields through the reactions between 2-methylquinolines and aldehydes under air.
- Mao, Dan,Hong, Gang,Wu, Shengying,Liu, Xin,Yu, Jianjun,Wang, Limin
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p. 3009 - 3019
(2014/05/20)
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- Metal-free oxidative olefination of primary amines with benzylic C-H bonds through direct deamination and C-H bond activation
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An oxidative olefination reaction between aliphatic primary amines and benzylic sp3 C-H bonds has been achieved using N-bromosuccinimide as catalyst and tert-butyl hydroperoxide as oxidant. The olefination proceeds under mild metal-free conditions through direct deamination and benzylic C-H bond activation, and provides easy access to biologically active 2-styrylquinolines with (E)-configuration. This journal is the Partner Organisations 2014.
- Gong, Liang,Xing, Li-Juan,Xu, Tong,Zhu, Xue-Ping,Zhou, Wen,Kang, Ning,Wang, Bin
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supporting information
p. 6557 - 6560
(2014/08/18)
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- Regiospecific C-N photocyclization of 2-styrylquinolines
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Regiospecific C-N photocyclization of 2-styrylquinolines resulting in formation of potentially biologically active quino[1,2-a]quinolizinium derivatives was investigated. The presence of strong electron-donating groups in the phenyl ring reveals to be a crucial factor managing photocyclization effectiveness. Introduction of a crown ether moiety allows changing the photoreaction parameters by means of complexation with Mg(ClO4) 2.
- Gulakova, Elena N.,Berdnikova, Daria V.,Aliyeu, Tseimur M.,Fedorov, Yuri V.,Godovikov, Ivan A.,Fedorova, Olga A.
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p. 5533 - 5537
(2014/07/08)
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- Oxidative olefination of secondary amines with carbon nucleophiles
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An unprecedented olefination reaction of secondary amines with carbon nucleophiles has been developed through C-N/C-H functionalization under metal-free oxidative conditions. In the presence of a stoichiometric amount of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), a range of secondary N-alkylanilines smoothly underwent oxidative olefination with 2-alkylazaarenes, acetophenone, and malononitrile to give structurally diverse polysubstituted alkenes in moderate to excellent yields with excellent (E) selectivity. Preliminary mechanistic studies revealed that the oxidative olefination reaction proceeds through amine oxidation followed by imine olefination. A range of secondary N-alkylanilines smoothly underwent DDQ-promoted oxidative olefination with 2-alkylazaarenes, acetophenone, and malononitrile to give structurally diverse alkenes in moderate to excellent yields with excellent (E) selectivity. Mechanistically, the reaction proceeds through amine oxidation followed by imine olefination (DDQ = 2,3-dichloro-5,6-dicyano-1,4-benzoquinone). Copyright
- Zhang, Yong-Gang,Xu, Jing-Kun,Li, Xi-Ming,Tian, Shi-Kai
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supporting information
p. 3648 - 3652
(2013/07/19)
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- Microwave-assisted solvent-free synthesis of 2-styrylquinolines in the presence of zinc chloride
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An efficient solvent-free procedure has been developed for the synthesis of (E)-2-styrylquinoline derivatives under microwave irradiation in the presence of zinc chloride. The developed procedure is advantageous due to shorter reaction time and simpler wo
- Li,Gavrishova,Budyka
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p. 823 - 828
(2012/11/13)
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- FeCl3?6H2O-catalyzed intramolecular allylic amination: Synthesis of substituted dihydroquinolines and quinolines
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A facile and efficient method to synthesize 2- or 4-substituted 1,2-dihydroquinolines and quinolines catalyzed by FeCl3?6H 2O (2 mol %) was described. The iron-catalyzed intramolecular allylic amination of 2-aminophenyl-1-en-3-ols proceeded smoothly to afford 13 1,2-dihydroquinoline and 8 quinoline derivatives under mild reaction conditions with good to excellent yields (up to 96%).
- Wang, Zhiming,Li, Shen,Yu, Bin,Wu, Haibo,Wang, Yurong,Sun, Xiaoqiang
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p. 8615 - 8620
(2012/11/07)
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- A catalyst-free benzylic C-H bond olefination of azaarenes for direct mannich-like reactions
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A highly efficient synthesis of trans-alkenylazaarene under catalyst-free conditions was developed via the addition of methylazaarenes to N-sulfonyl aldimines and a subsequent C-N elimination in situ. A one-pot procedure for this addition-elimination was also developed. The reaction could tolerate a broad substrate scope and give the corresponding alkenylazaarenes in high yields.
- Yan, Yizhe,Xu, Kun,Fang, Yang,Wang, Zhiyong
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scheme or table
p. 6849 - 6855
(2011/10/04)
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- Oxime palladacycle-catalyzed Suzuki-Miyaura alkenylation of aryl, heteroaryl, benzyl, and allyl chlorides under microwave irradiation conditions
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A simple new protocol for the palladium-catalyzed Suzuki-Miyaura cross-coupling of organic chlorides under microwave irradiation is presented. Deactivated aryl and heteroaryl chlorides are efficiently cross-coupled with alkenylboronic acids and potassium alkenyltrifluoroborates using the 4,4′-dichlorobenzophenone oxime-derived palladacycle 1b as precatalyst in 0.1 to 0.5 mol% palladium loading, tris(tert-butyl)phosphonium tetrafluoroborate {[HP(t-Bu)3]BF4} as ligand, tetra-n-butylammonium hydroxide as cocatalyst, and potassium carbonate as base in N,N- dimethylformamide at 130°C under microwave irradiation conditions. Under these conditions, styrenes, stilbenes, and alkenylarenes are obtained in good to high yields, and with high regio- and diastereoselectivities in only 20 min. The reported protocol is also very efficient for the regioselective alkenylation of benzyl and allyl chlorides to afford allylarenes and 1,4-dienes. Copyright
- Civicos, Jose F.,Alonso, Diego A.,Najera, Carmen
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supporting information; experimental part
p. 1683 - 1687
(2011/09/19)
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- One-pot friedlnder quinoline synthesis: Scope and limitations
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A highly effective one-pot Friedlnder quinoline synthesis from o-nitroarylcarbaldehydes and ketones or aldehydes was developed and the scope and limitations of the method were examined. The o-nitroarylcarbaldehydes were reduced to o-aminoarylcarbaldehydes with iron in the presence of a catalytic amount of aqueous hydrochloric acid; the amino compounds were then condensed in situ with ketones or aldehydes to form mono- or disubstituted quinolines, respectively, in good-to-excellent yields (58-100%). Georg Thieme Verlag Stuttgart - New York.
- Li, An-Hu,Beard, David J.,Coate, Heather,Honda, Ayako,Kadalbajoo, Mridula,Kleinberg, Andrew,Laufer, Radoslaw,Mulvihill, Kristen M.,Nigro, Anthony,Rastogi, Pawan,Sherman, Dan,Siu, Kam W.,Steinig, Arno G.,Wang, Ti,Werner, Doug,Crew, Andrew P.,Mulvihill, Mark J.
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experimental part
p. 1678 - 1686
(2010/06/22)
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- A highly effective one-pot synthesis of quinolines from o-nitroarylcarbaldehydes
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A simple and an efficient one-pot quinoline synthesis using inexpensive and readily available reagents was proposed. The solids were removed by filtration and the filtrate was treated with ketone and powdered KOH. The o-Nitroarylcarbaldehydes were reduced to aminocarbaldehydes with iron in the presence of catalytic HCl and subsequently condensed in situ with aldehydes or ketones to form mono- or di-substituted quinolines in high yields. The method can be used to prepare 2,3-disubstituted quinolines. A mixture of isomers was generated when an unsymmetrical ketone was used, which proved to be easily separable by silica gel column chromatography. The one-pot procedure is mild enough to allow a phenyl-substituted α,β-unsaturated ketone for using as a reactant under basic conditions in refluxing ethanol without significant competition from 1,4-Michael addition. The method provides efficient means to synthesize biologically active natural and unnatural quinoline-derived compounds.
- Li, An-Hu,Ahmed, Eilaf,Chen, Xin,Cox, Matthew,Crew, Andrew P.,Dong, Han-Qing,Jin, Meizhong,Ma, Lifu,Panicker, Bijoy,Siu, Kam W.,Steinig, Arno G.,Stolz, Kathryn M.,Tavares, Paula A. R.,Volk, Brian,Weng, Qinghua,Werner, Doug,Mulvihill, Mark J.
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- Multifunctional catalysis of a ruthenium-grafted hydrotalcite: One-pot synthesis of quinolines from 2-aminobenzyl alcohol and various carbonyl compounds via aerobic oxidation and aldol reaction
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The Ru-grafted hydrotalcite was found to be an excellent multifunctional catalyst for one-pot synthesis of quinolines from 2-aminobenzyl alcohol and various carbonyl compounds. These quinolines were obtained through aerobic oxidation by the Ru species, followed by aldol reaction on base sites of the hydrotalcite.
- Motokura, Ken,Mizugaki, Tomoo,Ebitani, Kohki,Kaneda, Kiyotomi
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p. 6029 - 6032
(2007/10/03)
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