- Ruthenium complex and preparation method thereof and catalytic application
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The invention discloses a ruthenium complex and a preparation method thereof and catalytic application. The ruthenium complex is reported for the first time. Research finds that the ruthenium complexhas the activity of catalytically synthesizing quinazoline and derivatives thereof or catalytically synthesizing quinoline and derivatives thereof. When the ruthenium complex provided by the inventionis used for catalytic synthesis of quinazoline and derivatives thereof or quinoline and derivatives thereof, the ruthenium complex has the advantages of mild reaction conditions, wide substrate range, high catalytic product yield and good functional group tolerance, and is significantly superior to the prior art.
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Paragraph 0104-0106; 0137-0138
(2021/01/24)
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- Ruthenium-catalyzed acceptorless dehydrogenative coupling of o-aminobenzyl alcohols with ketones to quinolines in the presence of carbonate salt
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A ruthenium complex bearing a functional 2,2′-bibenzimidazole ligand [(p-cymene)Ru(BiBzImH2)Cl][Cl] was designed, synthesized and found to be a general and highly efficient catalyst for the synthesis of quinolines via acceptorless dehydrogenative coupling of o-aminobenzyl alcohols with ketones in the presence of carbonate salt. It was confirmed that NH units in the ligand are crucial for catalytic activity. The application of this catalytic system for the scale-gram synthesis of biologically active molecular was also undertaken. Notably, this research exhibits new potential of metal–ligand bifuctional catalysts for acceptorless dehydrogenative reactions.
- Xu, Xiangchao,Ai, Yao,Wang, Rongzhou,Liu, Liping,Yang, Jiazhi,Li, Feng
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p. 340 - 349
(2021/02/27)
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- A cobalt-catalyzed method for synthesizing quinoline and quinazoline compounds
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The present invention discloses a cobalt-catalyzed synthesis of quinoline and quinazoline compounds, by a benzene compound with amino and hydroxyl groups or benzonitrile compounds as raw materials, in the presence of a catalyst and a base by a receptor-fr
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Paragraph 0011; 0052
(2022/01/10)
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- Efficient access to quinolines and quinazolines by ruthenium complexes catalyzed acceptorless dehydrogenative coupling of 2-aminoarylmethanols with ketones and nitriles
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Treatment of N,N,O-tridentate pyrazolyl-pyridinyl-alcohol ligands, 2-(CR1R2OH)-6-[3,5-(R3)2C3HN2]C5H3N (R1 = R2 = Me, R3 = H (L1H); R1 = Me, R2 = Ph, R3 = H (L2H); R1 = R2 = Ph, R3 = H (L3H); R1 = R2 = R3 = Me (L4H)) with RuCl3?xH2O in refluxing EtOH afforded the corresponding Ru(III) complexes L2RuCl (1a-1d), which were well characterized by IR, HR-MS and X-ray single crystal structural determination. These Ru complexes showed similarly high catalytic performance for both dehydrogenative couplings of 2-aminoarylmethanols with ketones and nitriles, giving the quinolines and quinazolines in good to excellent yields. This protocol provides an atom-economical and sustainable route to access various structurally important quinoline and quinazoline derivatives by using phosphine-free ligand based Ru catalysts.
- Feng, Qi,Han, Zhangang,Hao, Zhiqiang,Huo, Shuaicong,Kong, Siqi,Lin, Jin,Lu, Guo-Liang,Zeng, Guang
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- Visible-Light-Mediated Oxidative Cyclization of 2-Aminobenzyl Alcohols and Secondary Alcohols Enabled by an Organic Photocatalyst
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This paper describes a visible-light-mediated oxidative cyclization of 2-aminobenzyl alcohols and secondary alcohols to produce quinolines at room temperature. This photocatalytic method employed anthraquinone as an organic small-molecule catalyst and DMSO as an oxidant. According to this present procedure, a series of quinolines were prepared in satisfactory yields.
- Xu, Jing-Xiu,Pan, Nan-Lian,Chen, Jia-Xi,Zhao, Jin-Wu
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p. 10747 - 10754
(2021/08/16)
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- Modular Access to Spiro-dihydroquinolines via Scandium-Catalyzed Dearomative Annulation of Quinolines with Alkynes
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The catalytic enantioselective construction of three-dimensional molecular architectures from planar aromatics such as quinolines is of great interest and importance from the viewpoint of both organic synthesis and drug discovery, but there still exist many challenges. Here, we report the scandium-catalyzed asymmetric dearomative spiro-annulation of quinolines with alkynes. This protocol offers an efficient and selective route for the synthesis of spiro-dihydroquinoline derivatives containing a quaternary carbon stereocenter with an unprotected N-H group from readily accessible quinolines and diverse alkynes, featuring high yields, high enantioselectivity, 100% atom-efficiency, and broad substrate scope. Experimental and density functional theory studies revealed that the reaction proceeded through the C-H activation of the 2-aryl substituent in a quinoline substrate by a scandium alkyl (or amido) species followed by alkyne insertion into the Sc-aryl bond and the subsequent dearomative 1,2-addition of the resulting scandium alkenyl species to the C=N unit in the quinoline moiety. This work opens a new avenue for the dearomatization of quinolines, leading to efficient and selective construction of spiro molecular architectures that were previously difficult to access by other means.
- Lou, Shao-Jie,Luo, Gen,Yamaguchi, Shigeru,An, Kun,Nishiura, Masayoshi,Hou, Zhaomin
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supporting information
p. 20462 - 20471
(2021/12/03)
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- Mild and efficient copper-catalyzed oxidative cyclization of oximes with 2-aminobenzyl alcohols at room temperature: synthesis of polysubstituted quinolines
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A simple and efficient ligand-free Cu-catalyzed protocol for the synthesis of polysubstituted quinolinesviaoxidative cyclization of oxime acetates with 2-aminobenzyl alcohols at room temperature has been developed. The presented approach provides a new synthetic pathway leading to polysubstituted quinolines with good functional group tolerance under mild conditions. Moreover, this transformation can be applied for the preparation of quinolines on a gram scale. Oxime acetates serve as the internal oxidants in the reactions, thus making this method very attractive.
- Liu, Yan-Yun,Wei, Yang,Huang, Zhi-Hui,Liu, Yilin
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supporting information
p. 659 - 666
(2021/02/06)
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- Iron Single Atom Catalyzed Quinoline Synthesis
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The production of high-value chemicals by single-atom catalysis is an attractive proposition for industry owing to its remarkable selectivity. Successful demonstrations to date are mostly based on gas-phase reactions, and reports on liquid-phase catalysis are relatively sparse owing to the insufficient activation of reactants by single-atom catalysts (SACs), as well as, their instability in solution. Here, mechanically strong, hierarchically porous carbon plates are developed for the immobilization of SACs to enhance catalytic activity and stability. The carbon-based SACs exhibit excellent activity and selectivity (≈68%) for the synthesis of substituted quinolines by a three-component oxidative cyclization, affording a wide assortment of quinolines (23 examples) from anilines and acetophenones feedstock in an efficient, atom-economical manner. Particularly, a Cavosonstat derivative can be synthesized through a one-step, Fe1-catalyzed cyclization instead of traditional Suzuki coupling. The strategy is also applicable to the deuteration of quinolines at the fourth position, which is challenging by conventional methods. The synthetic utility of the carbon-based SAC, together with its reusability and scalability, renders it promising for industrial scale catalysis.
- Chen, Zhongxin,Song, Jingting,Peng, Xinwen,Xi, Shibo,Liu, Jia,Zhou, Wenhui,Li, Runlai,Ge, Rile,Liu, Cuibo,Xu, Haisen,Zhao, Xiaoxu,Li, Haohan,Zhou, Xin,Wang, Lu,Li, Xing,Zhong, Linxin,Rykov, Alexandre I.,Wang, Junhu,Koh, Ming Joo,Loh, Kian Ping
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- Enantioselective Synthesis of Tetrahydroquinolines via One-Pot Cascade Biomimetic Reduction?
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A novel and efficient protocol for the synthesis of chiral tetrahydroquinoline derivatives with excellent enantioselectivities and high yields has been developed through one-pot cascade biomimetic reduction. The detailed reaction pathway includes the acid-catalyzed and ruthenium-catalyzed formation of aromatic quinoline intermediates and biomimetic asymmetric reduction.
- Zhao, Zi-Biao,Li, Xiang,Chen, Mu-Wang,Wu, Bo,Zhou, Yong-Gui
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p. 1691 - 1695
(2020/11/03)
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- Efficient Organoruthenium Catalysts for α-Alkylation of Ketones and Amide with Alcohols: Synthesis of Quinolines via Hydrogen Borrowing Strategy and their Mechanistic Studies
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A new family of phosphine free organometallic ruthenium(II) catalysts (Ru1–Ru4) supported by bidentate NN Schiff base ligands (L1–L4 where L1=N,N-dimethyl-4-((2-phenyl-2-(pyridin-2-ylmethyl)hydrazineylidene)methyl) aniline, L2=N,N-diethyl-4-((2-phenyl-2-(pyridin-2-ylmethyl)hydrazineylidene)methyl)aniline, L3=N,N-dimethyl-4-((2-phenyl-2-(pyridin-2-yl)hydrazineylidene)methyl)- aniline and L4=N,N-diethyl-4-((2-phenyl-2-(pyridin-2-yl)hydrazineylidene)methyl) aniline) was prepared and characterized. These half-sandwich complexes acted as catalysts for C?C bond formation and exhibited excellent performance in the dehydrogenative coupling of ketones and amides. In the synthesis of C–C bonds, alcohols were utilized as the alkylating agent. A broad range of substrates, including sterically hindered ketones and alcohols, were well tolerated under the optimized conditions (TON up to 47000 and TOF up to 11750 h?1). This ruthenium (II) catalysts were also active towards the dehydrogenative cyclization of o-amino benzyl alcohol for the formation of quinolines derivatives. Various polysubstituted quinolines were synthesized in moderate to excellent yields (TON up to 71000 and TOF up to 11830 h?1). Control experiments were carried out and the ruthenium hydride intermediate was characterized to support the reaction mechanism and a probable reaction pathway of dehydrogenative coupling for the C?C bond formation has been proposed.
- Maji, Ankur,Singh, Anshu,Singh, Neetu,Ghosh, Kaushik
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p. 3108 - 3125
(2020/05/18)
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- Sustainable synthesis of quinolines (pyridines) catalyzed by a cheap metal Mn(I)-NN complex catalyst
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This study represents the first example of a bidentate phosphine-free manganese(I)-NN complex catalyst for the synthesis of quinolines (pyridines) through acceptorless dehydrogenative condensation of various secondary alcohols with amino alcohols. The coupling reactions occurred at 3 mol% catalyst loading and 110°C, and tolerated diverse functional groups. Moderate to excellent yields ranging from 45% to 89% were achieved after 12 hr of reaction. The present protocol provides a concise and environmentally friendly method for the construction of heterocyclic compounds.
- Chai, Huining,Tan, Weiqiang,Lu, Yuanyuan,Zhang, Guangyao,Ma, Jiping
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- The synthesis of quinolines: via denitrogenative palladium-catalyzed cascade reaction of o -aminocinnamonitriles with arylhydrazines
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The first example of the palladium-catalyzed cascade reaction of o-aminocinnamonitriles with arylhydrazines has been achieved, providing an efficient synthetic pathway to access quinolines with moderate to good yields. Preliminary mechanistic experiments
- Chen, Jiuxi,Huang, Hang,Li, Renhao,Xie, Jing,Xu, Tong,Ye, Xueting
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p. 8586 - 8593
(2020/03/13)
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- N-Heterocyclic carbene copper catalyzed quinoline synthesis from 2-aminobenzyl alcohols and ketones using DMSO as an oxidant at room temperature
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A facile and practical process for the synthesis of quinolines through an N-heterocyclic carbene copper catalyzed indirect Friedl?nder reaction from 2-aminobenzyl alcohol and aryl ketones using DMSO as an oxidant at room temperature is reported. A series of quinolines were synthesized in acceptable yields.
- Xu, Jingxiu,Chen, Qingmao,Luo, Zhigao,Tang, Xiaodong,Zhao, Jinwu
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p. 28764 - 28767
(2019/09/30)
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- Synthesis of 2-Arylisoindoline Derivatives Catalyzed by Reusable 1,2,4-Triazole Iridium on Mesoporous Silica through a Cascade Borrowing Hydrogen Strategy
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Covalent attachment of a 1,2,4-triazole iridium complex to mesoporous MCM-41 generated a heterogeneous catalyst that was found to be effective in the synthesis of 2-aryl isoindolines, quinolines, cyclic amines, and symmetrical secondary amines through a cascade borrowing hydrogen strategy. Interestingly, the supported heterogeneous iridium catalyst prepared from the 1,2,4-triazole iridium complex and mesoporous MCM-41 exhibited high catalytic activity in the preparation of 2-aryl isoindoline derivatives and symmetrical secondary amines. The catalyst system is highly recyclable for at least five times. Besides the important effect of the triazole, iridium sites grafted on siliceous supports can act as multifunctional catalytic centers and thus greatly enhance the catalytic activity of the catalysts. Furthermore, mechanistic experiments revealed that the reaction is initiated by an initial alcohol dehydrogenation and promoted by an iridium hydride intermediate. Importantly, the direct detection of a diagnostic iridium hydride signal confirmed that the synthesis of 2-aryl isoindolines occurs by a borrowing hydrogen process. This work provides an efficient example of isoindolines synthesis through a borrowing hydrogen strategy.
- Yao, Wei,Ge, Chenyang,Zhang, Yilin,Xia, Xiao-Feng,Wang, Long,Wang, Dawei
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supporting information
p. 16099 - 16105
(2019/11/26)
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- Unsymmetrical triazolyl-naphthyridinyl-pyridine bridged highly active copper complexes supported on reduced graphene oxide and their application in water
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A novel unsymmetrical triazolyl-naphthyridinyl-pyridine ligand was designed and synthesized, and employed in the synthesis of a heterogeneous copper complex on reduced graphene oxide. The resulting copper composite was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX). This supported copper catalyst containing unsymmetrical triazolyl-naphthyridinyl-pyridine (only 0.1 mol%) showed excellent catalytic activity in water with good recyclability. Various functionalized quinoline derivatives were successfully synthesized in high yields through the green strategy in water. Other heterocyclic compounds, such as pyridine, 2-(pyridin-2-yl)quinoline, 1,8-naphthyridine, 5,6-dihydronaphtho[1,2-b][1,8]naphthyridine and 2-(pyridin-2-yl)-1,8-naphthyridine derivatives, were achieved in water with more than 80% yields. Mechanism studies revealed that this transformation occurs via dehydrogenation, condensation, and transfer hydrogenation and dehydrogenation processes which was supported by a deuterium labeling experiment.
- Hu, Wenkang,Zhang, Yilin,Zhu, Haiyan,Ye, Dongdong,Wang, Dawei
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supporting information
p. 5345 - 5351
(2019/10/11)
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- Synthesis of quinolines via acceptorless dehydrogenative tandem cyclization of 2-amionbenzyl alcohol with alcohols using magnetic CuNiFeO nanocatalyst
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This work reports the preparation of nano CuNiFeO and its application in the synthesis of quinolines. The prepared nanocatalyst was characterized using various characterization techniques such as XRD, FEG-SEM, EDX, HR-TEM and XPS. Nano CuNiFeO as a heterogeneous catalyst shows a very high efficiency towards double dehydrogenation tandem cyclization reaction of 2-amionbenzyl alcohol with alcohols resulting into a simple, sustainable and environment friendly synthesis of quinolines. Due to the magnetic property associated with nanocatalyst, it was easily separated from the reaction mixture using external magnet and could be reused up to five cycles. To the best of our knowledge, this is for the first time a heterogenous magnetic CuNiFeO nanocatalyst is being reported for this reaction.
- Chaurasia, Shivkumar R.,Tiwari, Abhishek R.,Bhanage, Bhalchandra M.
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- Arylquinoline derivative synthesis method
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The invention belongs to the technical field of organic synthesis, and specifically relates to an arylquinoline derivative synthesis method, wherein the synthesis of arylquinoline derivatives with diversified structures is achieved through palladium-catalyzed continuous carbon-carbon/carbon-nitrogen bond construction, and specifically a 2-arylquinoline derivative is prepared by using a compound (E)-3-(2-aniline)acrylonitrile and arylboronic acid as raw materials under a palladium catalyst system. According to the present invention, the method has characteristics of wide raw material source oreasy preparation, simple operation, controllable selectivity, high yield, mild conditions and wide applicability.
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Paragraph 0053-0056
(2019/11/29)
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- Pd-Catalyzed Tandem Reaction of 2-Aminostyryl Nitriles with Arylboronic Acids: Synthesis of 2-Arylquinolines
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A novel palladium-catalyzed protocol for the synthesis of 2-arylquinolines via tandem reaction of 2-aminostyryl nitriles with arylboronic acids has been developed with good functional group tolerance. The presented approach offers a new synthetic pathway toward the core structures of 2-arylquinolines compared to classical condensation reaction of (E)-2-aminostyryl aryl ketones. Moreover, the present synthetic route could be readily scaled up to gram quantity without difficulty. Preliminary mechanistic experiments showed that this transformation involves a nucleophilic addition of aryl palladium species to the nitrile to generate an aryl ketone intermediate followed by an intramolecular cyclization and dehydration to quinoline ring.
- Xu, Tong,Shao, Yinlin,Dai, Ling,Yu, Shulin,Cheng, Tianxing,Chen, Jiuxi
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p. 13604 - 13614
(2019/10/16)
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- Facile synthesis of substituted quinolines by iron(iii)-catalyzed cascade reaction between anilines, aldehydes and nitroalkanes
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A library of substituted quinolines has been synthesized by the reaction of aldehydes, anilines and nitroalkanes using a catalytic amount of Fe(iii) chloride. The reaction is a simple, efficient, one-pot, three-component domino strategy in ambient air which afforded the products in high yields. A probable pathway of the reaction is a sequential aza-Henry reaction/cyclization/denitration. The use of commercially available chemicals as starting materials, an inexpensive metal catalyst, aerobic reaction conditions, tolerance of a wide range of functional groups, and operational simplicity are the notable advantages of this present protocol.
- Mahato, Sachinta,Mukherjee, Anindita,Santra, Sougata,Zyryanov, Grigory V.,Majee, Adinath
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p. 7907 - 7917
(2019/09/06)
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- Synthesis of 2-Substituted Quinolines from 2-Aminostyryl Ketones Using Iodide as a Catalyst
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A new protocol for the synthesis of 2-substituted quinolines from 2-aminostyryl ketones has been developed using iodide as a nucleophilic catalyst. Conjugate addition of iodide to 2-aminostyryl ketones yielded the corresponding β-iodoketones, which could have a conformation where the amino and carbonyl groups are proximal through free rotation about the Cα-Cβ single bond. Subsequent condensation between the amino and carbonyl groups followed by elimination of hydrogen iodide provided the corresponding quinolines, with regeneration of the iodide catalyst.
- Lee, So Young,Jeon, Jiye,Cheon, Cheol-Hong
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p. 5177 - 5186
(2018/05/15)
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- On-Water Synthesis of 2-Substituted Quinolines from 2-Aminochalcones Using Benzylamine as the Nucleophilic Catalyst
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On-water synthesis of 2-substituted quinolines from 2-aminochalcone derivatives was developed using benzylamine as the nucleophilic catalyst. Various 2-aminochalcones could be applied to this protocol, and the desired 2-substituted quinoline products were isolated in excellent yields by simple filtration. Furthermore, we elucidated the role of benzylamine in this transformation and provided the detailed reaction mechanism. This protocol has several additional advantages, such as simple operation, broad substrate scope, good functional group tolerance, easy product isolation, recycling of the catalyst, and gram-scale synthesis.
- Lee, So Young,Cheon, Cheol-Hong
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p. 13036 - 13044
(2018/11/20)
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- A nickel catalyzed acceptorless dehydrogenative approach to quinolines
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A general, efficient and environmentally benign, one-step synthesis of substituted quinoline derivatives was achieved by acceptorless dehydrogenative coupling of o-aminobenzylalcohols with ketones and secondary alcohols catalyzed by a cheap, earth abundant and easy to prepare nickel catalyst [Ni(MeTAA)], featuring a tetraaza macrocyclic ligand (tetramethyltetraaza[14]annulene (MeTAA)). A wide variety of substituted quinolines were synthesized in high yields starting from readily available o-aminobenzylalcohols and ketones or secondary alcohols. A few controlled reactions were carried out to establish the acceptorless dehydrogenative nature of the reactions.
- Parua, Seuli,Sikari, Rina,Sinha, Suman,Das, Siuli,Chakraborty, Gargi,Paul, Nanda D.
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p. 274 - 284
(2018/01/12)
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- Method for synthesizing quinoline by oxidizing and cyclizing acetophenone and aniline compound
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The invention discloses a method for synthesizing quinoline by oxidizing and cyclizing acetophenone and aniline compound. According to the method, acetophenone, aniline compound and dimethyl sulfoxidegenerate one-pot reaction to obtain quinoline in an oxygen containing atmosphere under existence of a copper salt catalyst. The method enriches quinoline varieties, provides more intermediates for pharmaceutical synthesis and further has the advantages of wide raw material source, simple step, moderate reaction condition, high yield and benefit to industrial production.
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Paragraph 0041-0044; 0055; 0056; 0092-0096
(2018/03/26)
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- Synthesis method of polysubstituted quinoline
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The invention discloses a synthesis method of polysubstituted quinolone. The method comprises the step: in an oxygen-containing atmosphere, enabling acetophenone, an aniline compound and dimethyl sulfoxide to react in a pot in the presence of an iron salt and/or ferrous salt catalyst so as to obtain the polysubstituted quinolone. By adopting the method disclosed by the invention, the variety of quinolone derivatives is enriched and more intermediates are provided for medicine synthesis; the synthesis method has the advantages of wide raw material sources, simple steps, moderate reaction conditions and high yield and industrial production is facilitated.
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Paragraph 0042; 0043; 0044; 0045; 0046; 0093; 0094-0097
(2018/04/02)
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- Copper-Catalyzed Aerobic Oxidative Cyclization of Anilines, Aryl Methyl Ketones and DMSO: Efficient Assembly of 2-Arylquinolines
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A Cu-catalyzed C?H cyclization of simple anilines with ketones and DMSO as a one-carbon source has been developed. Using an aerobic oxidative protocol, a number of ketones and anilines could be easily converted to 2-arylquinolines, rather than 4-arylquinolines, thus providing a highly atom-economical and simple approach to biologically significant 2-arylquinolines. Based on the preliminary experiments, a plausible mechanism is proposed. (Figure presented.).
- Liu, Yufeng,Hu, Yuqun,Cao, Zhongzhong,Zhan, Xi,Luo, Weiping,Liu, Qiang,Guo, Cancheng
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supporting information
p. 2691 - 2695
(2018/06/04)
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- Molybdenum-Catalyzed Sustainable Friedl?nder Synthesis of Quinolines
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Polysubstituted quinolines have been efficiently synthesized from nitroarenes and glycols, as reducing agents, under dioxomolybdenum(VI)-catalysis. Interestingly, the waste reduction byproduct is incorporated into the final heterocycle. This method repres
- Rubio-Presa, Rubén,Suárez-Pantiga, Samuel,Pedrosa, María R.,Sanz, Roberto
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supporting information
p. 2216 - 2220
(2018/06/14)
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- Enantioselective Synthesis of Tetrahydroquinolines from 2-Aminochalcones via a Consecutive One-Pot Reaction Catalyzed by Chiral Phosphoric Acid
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A new asymmetric protocol for the synthesis of chiral tetrahydroquinolines from 2-aminochalcones via a two-step one-pot consecutive process (cyclization/asymmetric reduction) has been developed using chiral phosphoric acid as the sole catalyst. 2-Aminochalcones were converted into the corresponding quinolines through chiral phosphoric acid-catalyzed dehydrative cyclization, and the resultant quinolines were subsequently reduced to the chiral tetrahydroquinolines via chiral phosphoric acid-catalyzed asymmetric reduction with Hantzsch ester. Various 2-aminochalcones could be applicable to this protocol, and the desired tetrahydroquinolines were obtained in excellent yields and with excellent enantioselectivities. Furthermore, the utility of this protocol has been successfully demonstrated in the highly efficient synthesis of estrogen receptor modulator.
- Park, Do Young,Lee, So Young,Jeon, Jiye,Cheon, Cheol-Hong
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p. 12486 - 12495
(2018/10/24)
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- Inhibitors of the detoxifying enzyme of the phytoalexin brassinin based on quinoline and isoquinoline scaffolds
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The detoxification of the phytoalexin brassinin to indole-3-carboxaldehyde and S-methyl dithiocarbamate is catalyzed by brassinin oxidase (BOLm), an inducible fungal enzyme produced by the plant pathogen Leptosphaeria maculans. Twenty-six substituted quinolines and isoquinolines are synthesized and evaluated for antifungal activity against L. maculans and inhibition of BOLm. Eleven compounds that inhibit BOLm activity are reported, of which 3-ethyl-6-phenylquinoline displays the highest inhibitory effect. In general, substituted 3-phenylquinolines show significantly higher inhibitory activities than the corresponding 2-phenylquinolines. Overall, these results indicate that the quinoline scaffold is a good lead to design paldoxins (phytoalexin detoxification inhibitors) that inhibit the detoxification of brassinin by L. maculans.
- Pedras, M. Soledade C.,Abdoli, Abbas,Sarma-Mamillapalle, Vijay K.
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- Palladium-catalyzed synthesis of quinolines from allyl alcohols and anilines
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A process for quinoline synthesis through palladium-catalyzed oxidative cyclization of aryl allyl alcohols and anilines is described. This process works in the absence of acid, base and any other additive and has a broad substrate scope, tolerating electron-withdrawing groups such as nitryl, trifluoromethyl and so on. A series of quinolines are prepared in satisfactory yields.
- Xu, Jingxiu,Sun, Jing,Zhao, Jinwu,Huang, Bin,Li, Xiaohan,Sun, Yulun
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p. 36242 - 36245
(2017/08/02)
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- Three-Component Povarov Reaction with Alcohols as Alkene Precursors: Efficient Access to 2-Arylquinolines
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An atom-economic and efficient approach to the synthesis of 2-arylquinolines has been developed. The protocol involves an iron-catalysed cascade N-alkylation/aerobic oxidation/Povarov reaction, and the desired quinolines were prepared in moderate to excellent yields from readily accessible anilines, aldehydes, and EtOH/nPrOH, with water as the only side-product. The aniline substrates also act as a recyclable transfer medium for EtOH/nPrOH through an in-situ N-alkylation/oxidation process. This makes EtOH/nPrOH an economical and environmentally friendly precursor of alkenes as well as the solvent.
- Li, Xinjian,Xing, Qi,Li, Pan,Zhao, Jingjing,Li, Fuwei
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supporting information
p. 618 - 625
(2017/02/05)
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- Method for synthesizing quinoline derivative
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The invention discloses a method for synthesizing a quinoline derivative. The method comprises the specific steps of in a reaction container, adding ketone, aminobenzylmethanol, an iridium complex catalyst, alkaline and a solvent (water), carrying out reflux reaction on reaction mixture in air, and cooling to room temperature after reaction is ended; extracting by using ethyl acetate, carrying out rotary evaporation to remove a solvent, and then carrying out column separation to obtain a target compound. According to the method disclosed by the invention, a hydrogen binding agent or oxygen does not need to be used, the environment-friendly water is used as the reaction solvent and reflux is carried out for 12 hours in air. The reaction conforms to the requirement of green chemistry, so that the application prospect is wide.
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Paragraph 0131; 0132; 0133
(2017/12/27)
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- Coupling N-H Deprotonation, C-H Activation, and Oxidation: Metal-Free C(sp3)-H Aminations with Unprotected Anilines
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An intramolecular oxidative C(sp3)-H amination from unprotected anilines and C(sp3)-H bonds readily occurs under mild conditions using t-BuOK, molecular oxygen and N,N-dimethylformamide (DMF). Success of this process, which requires mildly acidic N-H bonds and an activated C(sp3)-H bond (BDE 85 kcal/mol), stems from synergy between basic, radical, and oxidizing species working together to promote a coordinated sequence of deprotonation: H atom transfer and oxidation that forges a new C-N bond. This process is applicable for the synthesis of a wide variety of N-heterocycles, ranging from small molecules to extended aromatics without the need for transition metals or strong oxidants. Computational results reveal the mechanistic details and energy landscape for the sequence of individual steps that comprise this reaction cascade. The importance of base in this process stems from the much greater acidity of transition state and product for the 2c,3e C-N bond formation relative to the reactant. In this scenario, selective deprotonation provides the driving force for the process.
- Evoniuk, Christopher J.,Gomes, Gabriel Dos Passos,Hill, Sean P.,Fujita, Satoshi,Hanson, Kenneth,Alabugin, Igor V.
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supporting information
p. 16210 - 16221
(2017/11/22)
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- Acrylamide in Rauhut-Currier reaction; intramolecular isomerization of activated alkenes for quinolone synthesis
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Acrylamides are fundamental Michael acceptors which have been used profoundly in synthetic, medicinal and polymer chemistry. However, due to their lower reactivity they have been least used in Morita-Baylis-Hillman (MBH) reaction and have been out of its vinylogus version Rauhut Currier (RC) reaction. Herein, use of acrylamide in RC reaction is being presented. Intramolecular RC reaction followed by [1,3]-H shift led to the synthesis of quinolone moiety. DABCO catalyzed IRC reaction of acrylamide at 80 °C in presence of water, was found to work on a number of precursors. En route chemo selective, gram scale method for ambiphilic, versatile precursor 2-amino chalcone is also reported. Chemoselective and economical conversion of 2-nitro chalcone to 2-aryl quinoline has also been developed.
- Bharadwaj, Kishor Chandra
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p. 5690 - 5699
(2017/08/26)
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- Preparation method of 2-phenylquinoline compounds
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The invention relates to a preparation method of 2-phenylquinoline compounds. The structural formula of the prepared 2-phenylquinoline compounds is shown in the description, and R1, R2, R3, R4, R5, R6, R7, R8 and R9 in the formula are a hydrogen atom, an alkyl group, an aryl group, an alkyloxy, a halogen or a trifluoromethyl group. The preparation method comprises the following steps: stirring o-nitrotoluene compounds, acetophenone compounds, an alkali and a solvent at a temperature from room temperature to 150 DEG C for 1-24 h; and carrying out quenching after a reaction ends, and carrying out organic solvent extraction, concentration and purification to obtain the 2-phenylquinoline compounds with the yield of 47-81%. The method has the characteristics of easily available raw materials, mild reaction conditions, short reaction time and simplicity in operation.
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Paragraph 0012
(2017/08/31)
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- A highly practical and convenient halogenation of fused heterocyclic N-oxides
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A novel, simple and practical method for the regioselective halogenation of fused heterocyclic N-oxides has been developed. It employs Vilsmeier reagent, generated in situ by POX3and DMF, as both the activating agent and the nucleophilic halide source. The method is amenable across a broad range of substrates, including quinolines, isoquinolines and the diazine N-oxides, possessing a variety of substitution patterns. Furthermore, all of the reagents associated are cheap and easy to obtain. The potential extension of this method to a one-pot oxidation/halogenation sequence that obviates the need for isolation of the N-oxide intermediates is also presented.
- Wang, Dong,Wang, Yuxi,Zhao, Junjie,Li, Linna,Miao, Longfei,Wang, Dong,Sun, Hua,Yu, Peng
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p. 5762 - 5768
(2016/08/30)
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- Synthesis of Quinolines via Iron-Catalyzed Redox Condensation of Alcohols with 2-Nitrobenzyl Methyl Ether/2-Nitrobenzyl Alcohols
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An iron-catalyzed redox condensation of 2-nitrobenzyl alcohols, formic acid, and alcohols has been developed, which affords substituted quinolines with carbon dioxide and water as the only side products. With the use of formic acid as a redox moderator to fill the electron gap of the global redox condensation process, the reaction goes smoothly with a smaller amount of alcohol in comparison to previous reports (i.e. 1.2 equiv versus 3.3-4 equiv). The reaction goes equally well when 2-nitrobenzyl methyl ether was used instead of 2-nitrobenzyl alcohol under otherwise identical conditions, shedding a new light on the study of this quinoline synthetic method.
- Wang, Qi,Wang, Meirong,Li, Hui-Jing,Zhu, Shuai,Liu, Ying,Wu, Yan-Chao
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p. 3985 - 3995
(2016/11/11)
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- Palladium-Catalyzed Allylic C-H Oxidative Annulation for Assembly of Functionalized 2-Substituted Quinoline Derivatives
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An efficient and practical palladium-catalyzed aerobic oxidative approach to afford functionalized 2-substituted quinolines in moderate to good yields from readily available allylbenzenes with aniline is developed. The present annulation process has high functional-group tolerance and high atom economy, making it a valuable and practical method in synthetic and medicinal chemistry. Moreover, this transformation is supposed to proceed through oxidation of allylic C-H functionalization to form C-C and C-N bonds in one pot.
- Li, Chunsheng,Li, Jianxiao,An, Yanni,Peng, Jianwen,Wu, Wanqing,Jiang, Huanfeng
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p. 12189 - 12196
(2016/12/23)
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- Acceptorless Dehydrogenative Cyclization of o-Aminobenzyl Alcohols with Ketones to Quinolines in Water Catalyzed by Water-Soluble Metal-Ligand Bifunctional Catalyst [Cp?(6,6′-(OH)2bpy)(H2O)][OTf]2
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The strategy for acceptorless dehydrogenative cyclization of o-aminobenzyl alcohols with ketones to quinolines in water has been accomplished. In the presence of [Cp?Ir(6,6′-(OH)2bpy)(H2O)][OTf]2, a series of desirable products were obtained in high yields. Notably, this research exhibits the potential for the construction of heterocycles via acceptorless dehydrogenative reactions in water catalyzed by water-soluble metal-ligand bifunctional catalysts.
- Wang, Rongzhou,Fan, Hongjun,Zhao, Wei,Li, Feng
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supporting information
p. 3558 - 3561
(2016/08/16)
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- Double C-H amination by consecutive SET oxidations
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A new method for intramolecular C-H oxidative amination is based on a FeCl3-mediated oxidative reaction of anilines with activated sp3 C-H bonds. The amino group plays multiple roles in the reaction cascade: (1) as the activating group in single-electron-transfer (SET) oxidation process, (2) as a directing group in benzylic/allylic C-H activation at a remote position, and (3) internal nucleophile trapping reactive intermediates formed from the C-H activation steps. These multielectron oxidation reactions proceed with catalytic amounts of Fe(iii) and inexpensive reagents.
- Evoniuk, Christopher J.,Hill, Sean P.,Hanson, Kenneth,Alabugin, Igor V.
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supporting information
p. 7138 - 7141
(2016/06/09)
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- Iridium-catalyzed synthesis of quinolines from 2-aminobenzyl alcohols with secondary alcohols
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The quinoline derivatives were synthesized from 2-aminobenzyl alcohols and secondary alcohols by the direct one-step synthesis using the iridium complexes as catalyst. This efficient and easy method is suitable for all kinds of substituted quinolines.
- Yu,Yao,Hu,Wang
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p. 376 - 379
(2016/04/20)
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- An Unexpected Construction of 2-Arylquinolines from N-Cinnamylanilines through sp3 Ci-H Aerobic Oxidation Induced by a Catalytic Radical Cation Salt
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An unexpected reaction of cinnamylanilines was achieved through the radical cation salt-induced aerobic oxidation of sp3 C-H bonds, providing a series of 2-arylquinolines. The mechanistic study shows that the cinnamylaniline was oxidized to an imine, which was attacked by the aniline generated through decomposition of the corresponding imine. After further intramolecular cyclization and aromatization, 2-arylquinolines were obtained. This reaction provides a new method to construct 2-arylquinolines from readily accessible starting materials.
- Liu, Fang,Yu, Liangliang,Lv, Shiwei,Yao, Junjun,Liu, Jing,Jia, Xiaodong
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supporting information
p. 459 - 465
(2016/02/12)
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- Synthesis of quinoline derivatives by an improved D?ebner-von Miller reaction using a recyclable Ag(I)-exchanged Montmorillonite K10 catalyst
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The D?ebner-von Miller synthesis of quinolines under solvent-free conditions is described, catalyzed by recyclable Ag(I)-exchanged Montmorillonite K10. The desired products are obtained in good to excellent yields and the reaction accommodates both aromatic and aliphatic α,β-unsaturated aldehydes making this process an attractive method for the synthesis of substituted quinolines. In addition, the Ag(I)-exchanged Montmorillonite K10 catalyst can be recovered and reused up to 5 times with excellent activity.
- Jayram, Janeeka,Jeena, Vineet
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p. 2213 - 2224
(2017/02/10)
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- Convenient synthesis of quinolines from α-2-nitroaryl alcohols and alcohols via a ruthenium-catalyzed hydrogen transfer strategy
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A new and straightforward method for convenient synthesis of quinolines via a ruthenium-catalyzed hydrogen-transfer strategy has been demonstrated. By employing a commercially available ruthenium catalyst system, different α-2-nitroaryl alcohols were efficiently converted in combination with a variety of alcohols into various substituted products in reasonable to good yields upon isolation. The synthetic protocol is operationally simple with a broad substrate scope, and there is no need for the use of specialized reducing agents, making it a practical approach for versatile preparation of various quinoline derivatives.
- Xie, Feng,Zhang, Min,Chen, Mengmeng,Lv, Wan,Jiang, Huanfeng
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p. 349 - 353
(2015/03/05)
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- Facile synthesis of 2-substituted quinolines and 3-alkynyl-2-aryl-2H-Indazole via SnCl2-mediated reductive cyclization
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A rapid and efficient SnCl2·2H2O mediated synthesis of quinolines and indazoles has been developed using A3-coupling followed by reductive cyclization. The key highlights are the formation of quinoline in a one-pot fashion and indazole through N-N bond formation.
- Sudhapriya, Narayanasamy,Nandakumar, Avanashiappan,Perumal, Paramasivan Thirumalai
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p. 58476 - 58480
(2015/02/19)
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- Selective synthesis of quinolines and indoles: Sulfur-assisted or selenium-catalyzed reaction of β-(2-nitrophenyl)-α, β-unsaturated ketones with carbon monoxide
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A simple and selective synthetic method of quinolines and indoles by the reaction of β- (2-nitrophenyl)-α,β-unsaturated ketones with carbon monoxide was developed. When β-(2-nitrophenyl)- α,β-unsaturated ketones were allowed to react with carbon monoxide and water in the presence of a stoichiometric amount of sulfur or a catalytic amount of selenium, the corresponding quinolines were produced in moderate-to-good yields. On the other hand, in the absence of water, the indoles were produced by the selenium-catalyzed reaction of the β-(2-nitrophenyl)- α,β-unsaturated ketones with carbon monoxide.
- Umeda, Rui,Kouno, Hiroshi,Kitagawa, Takayuki,Okamoto, Tomohiro,Kawashima, Keisuke,Mashino, Tsukasa,Nishiyama, Yutaka
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p. 698 - 703
(2015/02/05)
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- Synthesis of substituted quinoline via copper-catalyzed one-pot cascade reactions of 2-bromobenzaldehydes with aryl methyl ketones and aqueous ammonia
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In this Letter, a new version of the Friedl?nder synthesis of quinoline derivatives starting from 2-bromobenzaldehydes, aryl methyl ketones, and aqueous ammonia with copper-catalyzed amination as a key step is presented. Remarkable advantages of this new quinoline synthesis include commercially available and economical starting materials, simple operational process, and excellent efficiency.
- Li, Bin,Guo, Chenhao,Fan, Xuesen,Zhang, Ju,Zhang, Xinying
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supporting information
p. 5944 - 5948
(2015/01/08)
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- Enantioselective cooperative triple catalysis: Unique roles of Au(i)/amine/chiral Bronsted acid catalysts in the addition/ cycloisomerization/transfer hydrogenation cascade
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An enantioselective cooperative process involving the concerted/ simultaneous action of three different catalysts i.e. Au(i)/amine/chiral Bronsted acid catalysts has been realized for the synthesis of 2-substituted tetrahydroquinolines from 2-aminobenzaldehydes and terminal alkynes.
- Patil, Nitin T.,Raut, Vivek S.,Tella, Ramesh Babu
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supporting information
p. 570 - 572
(2013/02/22)
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- Simple C-2-substituted quinolines and their anticancer activity
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Sixteen C-2-substituted quinolines were tested in both human cancer cell lines (MCF-7, H-460 and SF-268) and normal cell lines (Vero and THP-1). Preliminary results indicate that 2-α-furyl- and 2-γ-pyridinyl quinoline derivatives 1, 13 and 14 are active against three human cancer cell lines and, at the same time, were devoid of cytotoxic effect on normal cells. Biological activity and SAR results were compared with different molecular descriptors determined in silico using online available software, in an attempt to show a relationship with the possible mode of action of these quinoline derivatives.
- Kouznetsov, Vladimir V.,Rojas Ruiz, Fernando A.,Vargas Mendez, Leonor Y.,Gupta, Mahabir P.
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p. 680 - 686
(2012/09/22)
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- Catalytic arylation of a C-H bond in pyridine and related six-membered N-heteroarenes using organozinc reagents
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Despite significant advances in the catalytic direct arylation of heteroarenes, the application of this reaction to pyridines has been met with limited success. An oxidative nucleophilic arylation strategy has been developed to overcome this problem. Pyridine, pyrazine, quinolone, and related electron-deficient N-heteroarenes can be arylated at the most electrophilic site using the developed nickel-catalyzed reaction. This protocol serves as a complementary method to catalytic direct arylation reactions. Less is more: Pyridine, pyrazine, quinoline and related electron-deficient N-heteroarenes can be arylated at the most electrophilic site using organozinc reagents through nickel catalysis. This protocol serves as a complementary method to catalytic direct arylation reactions. Copyright
- Hyodo, Isao,Tobisu, Mamoru,Chatani, Naoto
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supporting information; experimental part
p. 1357 - 1365
(2012/08/08)
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- Mild and simple access to diverse 4-amino-substituted 2-phenyl-1,2,3,4- tetrahydroquinolines and 2-phenylquinolines based on a multicomponent imino diels-alder reaction
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A straightforward synthesis of new 1-(2-phenyl-1,2,3,4-tetrahydroquinolin- 4-yl) pyrrolidin-2-ones/azepan-2-one from N-vinyl caprolactam/N-vinylpyrrolidin- 2-one and N-benzylideneaniline via the imino Diels-Alder reaction has been reported for the first time. Antimony(III) chloride has been shown to effectively catalyze imino-Diels-Alder reaction to afford both 2-phenylquinoline and 2-phenyl-1,2,3,4-tetrahydroquinolin derivatives in excellent yields at ambient temperature. The cis diastereoselectivity to give cis 2-phenyl-1,2,3,4-tetrahydroquinolines is also highlighted in this reaction. Copyrigh
- Varma, P. Prabhakara,Sherigara, Bailure S.,Mahadevan, Kittappa M.,Hulikal, Vijaykumar
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experimental part
p. 2220 - 2231
(2010/09/15)
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