- 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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- Molybdatophosphoric acid/NaNO2/wet SiO2 as an efficient system for the aromatization of 1,2-dihydroquinolines under mild and heterogeneous conditions
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A combination of molybdatophosphoric acid and NaNO2 in the presence of wet SiO2 was used as an effective oxidizing agent for the oxidation of 1,2-dihydroquinolines to their corresponding quinoline derivatives in dichlomethane at room temperature with excellent yields. Copyright Taylor & Francis Group, LLC.
- Niknam, Khodabakhsh,Karami, Bahador,Molazadeh, Saghar,Pourkhosro, Azar
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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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- Rhodium-Catalyzed Dehydrogenative Annulation of N-Arylmethanimines with Vinylene Carbonate for Synthesizing Quinolines
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Here we report a novel Rh-catalyzed C-H/C-H alkenylation of N-arylmethanimines with vinylene carbonate acting as a vinylene unit. Forty examples of C3,C4-nonsubstituted quinolines were achieved from commercially available starting materials. This identified process features an exceedingly simple system, a lower loading of catalyst, and the capacity for postfunctionalization with bioactive molecules.
- Hu, Yan,Nan, Jiang,Yin, Jiacheng,Huang, Guanjie,Ren, Xin,Ma, Yangmin
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supporting information
p. 8527 - 8532
(2021/11/13)
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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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- 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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- 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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- Visible-light-induced photoxidation-Povarov cascade reaction: synthesis of 2-arylquinoline through alcohol andN-benzylanilines under mild conditionsviaAg/g-C3N4nanometric semiconductor catalyst
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With a Ag/g-C3N4nanometric semiconductor as the photocatalyst, 2-arylquinolines were synthesized through a photoxidation-Povarov cascade reaction ofN-benzylanilines and alcohols under visible light irradiation. Under the blue light of a 3 W LED, good yields were achieved for various substrates in oxygen at room temperature. This methodology provides a green and mild alternative for the formation of 2-arylquinoline derivatives. Remarkably, the Ag/g-C3N4nanocomposite can be conveniently recovered and reused several times with satisfying yields.
- Wang, Peng,Wang, Xiaowen,Niu, Xiyu,Zhu, Li,Yao, Xiaoquan
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supporting information
p. 4840 - 4843
(2020/05/13)
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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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- Preparation method and application of 2-aryl quinoline derivatives
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The invention discloses a preparation method and application of 2-aryl quinoline derivatives, and belongs to the technical field of novel organic synthesis methods. According to the preparation method, in a Schlenk tube with a screw cap, aromatic aldehyde and aromatic amine react with a cyclic ether compound under the action of a catalytic system composed of a copper salt, trifluoromethane sulfonic acid and air, and 2-aryl quinoline compounds are obtained. A cyclic ether compound is used as a dicarbon synthon for the first time, and a series of 2-aryl quinoline compounds are prepared. The preparation method has the advantages of mild reaction conditions, wide reaction substrate universality, short reaction time, high target product yield, and simple reaction operation and post-treatment process. The compounds have a wide application prospect in the field of medicinal chemistry.
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Paragraph 0020; 0042-0043
(2020/08/09)
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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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- Sustainable synthesis of N-heterocycles in water using alcohols following the double dehydrogenation strategy
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The present study describes the first example of synthesis of pharmaceutically relevant N-heterocycles like substituted quinolines, acridines and 1,8-naphthyridines in water under air using alcohols in presence of a new water soluble Ir-complex. The viability and efficiency of this approach was demonstrated by the efficient synthesis of biologically active natural product (±)-galipinine and gram scale synthesis of various N-heteroaromatics. Several kinetic experiments and DFT calculations were carried out to support the plausible reaction mechanism which disclosed that this system followed a concerted outer sphere mechanism for the dehydrogenation of alcohols.
- Maji, Milan,Chakrabarti, Kaushik,Panja, Dibyajyoti,Kundu, Sabuj
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- Ligand-controlled phosphine-free Co(II)-catalysed cross-coupling of secondary and primary alcohols
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Cobalt(II) complexes (5 mol% Co) bearing phosphine-free N?N?N pincer ligands efficiently catalyze C–C coupling of secondary and primary alcohols to selectively form α-alkylated ketones with a good functional group compatibility using NaOH (20 mol%) as a base at 120 °C. The NH group on the N?N?N–Co(II) precatalyst controls the activity and selectivity. This simple catalytic system is involved in the synthesis of quinolones via the dehydrogenative annulation of 2-aminobenzyl alcohols with secondary alcohols.
- Zhang, Shi-Qi,Guo, Bin,Xu, Ze,Li, Hong-Xi,Li, Hai-Yan,Lang, Jian-Ping
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- Phosphine Ligand-Free Ruthenium Complexes as Efficient Catalysts for the Synthesis of Quinolines and Pyridines by Acceptorless Dehydrogenative Coupling Reactions
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A series of phosphine-free Ru(III)/Ru(II) complexes of NH functionalized N?N?N pincer ligands exhibit excellent activity for acceptorless dehydrogenative coupling (ADC) of secondary alcohols with 2-aminobenzyl or γ-amino alcohols to quinolines and pyridines. Ru(III) complexes [LRuCl3] (L=6-(3-R1,5-R2-1H-pyrazol-1-yl)-N-(pyridin-2-yl)pyridin-2-amine; 1 a: R1=R2=H (L1); 1 b: R1=R2=Me (L2); 1 c: R1=H, R2=CF3 (L3); 1 d: R1=H, R2=Ph (L4); 1bMe: L=6-(3,5-dimethyl-1H-pyrazol-1-yl)-N-methyl-N-(pyridin-2-yl)pyridin-2-amine (L2Me)) were obtained by refluxing RuCl3 ? xH2O with the corresponding ligand in EtOH. Five Ru(II) complexes [LRu(DMSO-κS)Cl2] (2 a: L=L1; 2 b: L=L2; 2 c: L=L3; 2 d: L=L4; 2bMe: L=L2Me) were formed by reducing the corresponding Ru(III) complex in refluxing EtOH. The latter complexes could also be prepared directly by refluxing Ru(DMSO)4Cl2 with the corresponding ligand in EtOH. These Ru(III) and Ru(II) complexes, especially 1 b/2 b, exhibited high catalytic efficiency and broad functional group tolerance in ADC reactions of secondary alcohols with 2-aminobenzyl or γ-amino alcohols to quinolines and pyridines. A detail mechanistic study indicated the Ru(III) complex was reduced into the Ru(II) species, which is the active catalytic center for ADC via a Ru?H/N?H bifunctional outer-sphere mechanism. This protocol provides a reliable, atom-economical and environmentally benign procedure for C?N and C?C bond formation.
- Guo, Bin,Yu, Tian-Qi,Li, Hong-Xi,Zhang, Shi-Qi,Braunstein, Pierre,Young, David J.,Li, Hai-Yan,Lang, Jian-Ping
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p. 2500 - 2510
(2019/05/10)
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- Dehydrogenative Synthesis of Quinolines, 2-Aminoquinolines, and Quinazolines Using Singlet Diradical Ni(II)-Catalysts
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Simple, straightforward, and atom economic methods for the synthesis of quinolines, 2-aminoquinolines, and quinazolines via biomimetic dehydrogenative condensation/coupling reactions, catalyzed by well-defined inexpensive and easy to prepare singlet diradical Ni(II)-catalysts featuring two antiferromagnetically coupled singlet diradical diamine type ligands are described. Various polysubstituted quinolines, 2-aminoquinolines, and quinazolines were synthesized in moderate to good yields from different low-cost and readily accessible starting materials. Several control experiments were carried out to get insight into the reaction mechanism which shows that the nickel and the coordinated diamine ligands participate in a synergistic way during the dehydrogenation of alcohols.
- Chakraborty, Gargi,Sikari, Rina,Das, Siuli,Mondal, Rakesh,Sinha, Suman,Banerjee, Seemika,Paul, Nanda D.
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p. 2626 - 2641
(2019/02/26)
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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 0049-0052
(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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- 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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- 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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- 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; 0062-0066
(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; 0063; 0064-0067
(2018/04/02)
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- Divergent Synthesis of Functionalized Quinolines from Aniline and Two Distinct Amino Acids
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A practicable quinoline synthesis from aniline and two amino acids was developed for generating a wide range of quinolines with high efficiency and diversity. Thus, it facilitated the creations of pharmaceutical derivatives, photochemical active compounds, and challenging scaffolds. The concept of using two amino acids as heterocyclic precursors has been raised for the first time. Mechanistic studies revealed that I2 enabled decarboxylation, oxidative deamination, and selective reconstruction of new C-N and C-C bonds processes.
- Xiang, Jia-Chen,Wang, Zi-Xuan,Cheng, Yan,Xia, Shi-Qing,Wang, Miao,Tang, Bo-Cheng,Wu, Yan-Dong,Wu, An-Xin
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p. 9210 - 9216
(2017/09/11)
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- Coupling Radical Homoallylic Expansions with C-C Fragmentations for the Synthesis of Heteroaromatics: Quinolines from Reactions of o-Alkenylarylisonitriles with Aryl, Alkyl, and Perfluoroalkyl Radicals
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Selective addition of radicals to isonitriles can be harnessed for initiating reaction cascades designed to overcome the stereoelectronic restrictions on homoallylic ring expansion in alkyne reactions and to develop a new general route for the preparation of N-heteroaromatics. This method utilizes alkenes as synthetic equivalents of alkynes by coupling homoallylic ring expansion to yield the formal "6-endo" products with aromatization via stereoelectronically assisted C-C bond scission. Computational analysis of the homoallyic expansion potential energy surface reveals that the indirect 5-exo/3-exo/retro-3-exo path is faster than the direct 6-endo-trig closure, revealing the general exo-preference for the cyclization processes.
- Evoniuk, Christopher J.,Gomes, Gabriel Dos Passos,Ly, Michelle,White, Frankie D.,Alabugin, Igor V.
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p. 4265 - 4278
(2017/04/27)
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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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- 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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- 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 0146; 0147; 0148
(2017/12/27)
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- Lewis acid-catalyzed borono-minisci reactions of arylboronic acids and heterocycles
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A Lewis acid-catalyzed Minisci reaction between arylboronic acids and heterocycles has been developed. This radical-coupling reaction was demonstrated employing several different heterocycles as well as electron-rich arylboronic acids. Quinoline substrates afforded modest regioselectivity for substitution at the 4-position under the reaction conditions, in contrast to previously reported Br?nsted acid-mediated reactions with quinoline substrates that favored substitution at the 2-position.
- Biaco, Joyce L.,Jones, Savannah L.,Barker, Timothy J.
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p. 1687 - 1697
(2016/10/12)
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- Synthesis of quinolines through copper-catalyzed intermolecular cyclization reaction from anilines and terminal acetylene esters
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A simple and convenient copper-catalyzed intermolecular cyclization reaction for the synthesis of quinolines from anilines and terminal acetylene esters has been developed. This methodology constructs the C-N and C-C bonds successively via a cascade process, and provides the desired products in moderate to good yields.
- Zheng, Zhilei,Deng, Guobo,Liang, Yun
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p. 103478 - 103481
(2016/11/13)
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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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- Method for preparing 2-aryl quinoline by cyclic ether compound
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The invention discloses a method for preparing 2-aryl quinoline by a cyclic ether compound, and belongs to the technical field of a novel organic synthesis method. The method comprises the following concrete process step: in a Schlenk tube with a screw cap, under the action of a catalytic system consisting of copper salt, trifluoromethanesulfonic acid and air, performing a reaction on aromatic aldehyde and aromatic amine and the cyclic ether compound to obtain 2-aryl quinoline compounds. In the reaction system, the cyclic ether compound is used as a two-carbon synthon for the first time so as to prepare a series of 2-aryl quinoline compounds. A preparation method disclosed by the invention has the advantages of mild reaction conditions, wide universality of reaction substrates, short reaction time, high yield of target products, simple reaction operation and aftertreatment process and the like.
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Paragraph 0041; 0042
(2016/10/09)
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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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- 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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- Iron-Based Imidazolium Salts as Versatile Catalysts for the Synthesis of Quinolines and 2- and 4-Allylanilines by Allylic Substitution of Alcohols
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Readily available iron(III)-based imidazolium salts have proven to be very versatile catalysts for the allylic substitution reaction of alcohols with anilines, allowing the synthesis of quinolines, 2-allylanilines and 4-allylanilines just by modulating the reaction conditions. Noteworthy, the formation of quinoline derivatives proceeds by ortho-allylation of the corresponding aniline and subsequent oxidative cyclization mediated by atmospheric oxygen. The reaction using anilines as nucleophiles is selective to the C-alkylation versus the N-alkylation, under any reaction conditions studied. (Figure presented.).
- Trillo, Paz,Pastor, Isidro M.
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p. 2929 - 2939
(2016/09/16)
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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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- Copper-Promoted Tandem Reaction of Azobenzenes with Allyl Bromides via N=N Bond Cleavage for the Regioselective Synthesis of Quinolines
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A copper-promoted tandem reaction of a variety of azobenzenes and allyl bromides via N=N bond cleavage to regioselectively construct quinoline derivatives has been developed. The azobenzenes act as not only construction units but also an oxidant for quinoline formation.
- Yi, Xiangli,Xi, Chanjuan
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p. 5836 - 5839
(2015/12/11)
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- ONO pincer type Pd(II) complexes: Synthesis, crystal structure and catalytic activity towards C-2 arylation of quinoline scaffolds
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Four new palladium(II) complexes featuring ONO pincer type hydrazone ligands were synthesized and characterized by spectroscopic and single-crystal XRD analysis. These complexes showed excellent catalytic activity towards the Suzuki-Miyaura cross coupling reaction of 2-chloroquinoline derivatives with various aryl boronic acids. The main advantages over previous methodologies include low catalyst loading, less problematic reaction media (H2O-DMF (80:20%)) and a lower reaction temperature of 60 °C for optimal performance.
- Arumugam, Vignesh,Kaminsky, Werner,Nallasamy, Dharmaraj
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p. 77948 - 77957
(2015/09/28)
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- Chiral phosphoric acid catalyzed oxidative kinetic resolution of cyclic secondary amine derivatives including tetrahydroquinolines by hydrogen transfer to imines
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A chiral Bronsted acid catalyzed dehydrogenative kinetic resolution of tetrahydroquinoline derivatives, which are representative of cyclic secondary amines, based on their hydrogen transfer to aromatic imines was efficiently achieved with high enantioselectivities. This hydrogen transfer of tetrahydroquinolines to imines was not driven by their aromatization to quinolines. This dehydrogenative kinetic resolution could be also applied to the asymmetric synthesis of various benzofused heterocycles containing secondary amine cores.
- Saito, Kodai,Miyashita, Hiromitsu,Akiyama, Takahiko
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supporting information
p. 16648 - 16651
(2015/11/25)
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- Coupling cyclizations with fragmentations for the preparation of heteroaromatics: Quinolines from o-alkenyl arylisocyanides and boronic acids
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Stereoelectronic restrictions on homoallylic ring expansion in alkyne cascades can be overcome by using alkenes as synthetic equivalents of alkynes in reaction cascades that are terminated by C-C bond fragmentation. Implementation of this approach using Mn(iii)-mediated reaction of o-alkenyl isocyanides and boronic acids leads to efficient synthesis of substituted quinolines.
- Evoniuk, Christopher J.,Ly, Michelle,Alabugin, Igor V.
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supporting information
p. 12831 - 12834
(2015/08/06)
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- Synthesis of polysubstituted quinolines via transition-metal-free oxidative cycloisomerization of o -cinnamylanilines
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An efficient synthesis of 2-aryl 4-substituted quinolines from stable and readily available o-cinnamylanilines, prepared from anilines and cinnamylalcohols, has been developed. The reaction occurred via a regioselective 6-endo-trig intramolecular oxidative cyclization using KOtBu as a mediator and DMSO as an oxidant at rt. The reaction showed a broad substrate scope with good to excellent yields.
- Rehan, Mohammad,Hazra, Gurupada,Ghorai, Prasanta
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p. 1668 - 1671
(2015/04/14)
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- Bronsted acid-mediated reactions of aldehydes with 2-vinylaniline and biphenyl-2-amine
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Herein we report simple Bronsted acid-mediated reactions of aldehydes with 2-vinylaniline and biphenyl-2-amine. Ultimately, the useful nitrogen-containing heterocycle derivatives are obtained. The electronic properties of the substituents on the aldehydes and 2-vinylaniline were investigated. It was found that molecules with both electron-donating and -withdrawing substituents were perfectly suitable substrates for this transformation, and the expected products were obtained in moderate to excellent yields.
- Zhang, Xu,Xu, Xuefeng,Yu, Lintao,Zhao, Qiang
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supporting information
p. 2280 - 2282
(2014/04/17)
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- An N-heterocyclic carbene-catalyzed approach to the indirect Friedl?nder quinoline synthesis
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Quinolines have been obtained through the indirect Friendl?nder annulation starting from 2-aminobenzyl alcohol or derivatives from it and ketones catalyzed by N-heterocyclic carbene, and the synthesis of polysubstituted quinolines through a one-pot, two-step tandem reaction starting from readily available ketones and alcohols via alpha-alkylation and indirect Friedl?nder annulation under air also has been presented.
- Zhu, Yanfang,Cai, Chun
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p. 52911 - 52914
(2015/02/05)
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- TMEDA-assisted effective direct ortho arylation of electron-deficient N -heteroarenes with aromatic grignard reagents
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In the addition of TMEDA in toluene, aryl Grignards could effectively and site-specifically ortho-arylate electron-deficient heteroarenes under mild conditions. This endeavor successfully changed the old low-yielding reaction, aryl Grignard addition to N-heteroarenes, into an efficient procedure for heterobiaryls. The combination of the inexpensive aryl Grignards, TMEDA, the cost-free air, no use of any transition-metal catalyst, the mild reaction conditions, and the high-yielding gram-scale results enables this new procedure to be cost-effective and potentially utilizable in industry.
- Zhuo, Fang-Fang,Xie, Wen-Wen,Yang, Yong-Xin,Zhang, Lei,Wang, Pei,Yuan, Rui,Da, Chao-Shan
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p. 3243 - 3249
(2013/06/26)
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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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- Synthesis of quinolines by a solid acid-catalyzed microwave-assisted domino cyclization-aromatization approach
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A microwave-assisted solid acid-catalyzed synthesis of quinolines from anilines and cinnamaldehydes is described. Use of montmorillonite K-10 results in a one-pot process; the cyclization and oxidation steps readily take place in a domino approach. Reactions were completed in a matter of minutes and provided excellent yields. The efficient and ecofriendly catalyst and the convenience of the product isolation make this process an attractive alternative for the synthesis of these important heterocycles.
- De Paolis, Omar,Teixeira, Liliana,T?r?k, Béla
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experimental part
p. 2939 - 2942
(2009/07/26)
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- In vitro antifungal activity of polyfunctionalized 2-(hetero)arylquinolines prepared through imino Diels-Alder reactions
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Diverse polyfunctionalized quinolines, easily prepared using Lewis acid-catalyzed imino Diels-Alder reactions between corresponding aldimines, were tested for antifungal properties against standardized as well as clinical isolates of clinically important fungi. Among them, 4-pyridyl derivatives displayed the best activities mainly against dermatophytes. The activity appears not to be related neither to the lipophilicity nor to the basicity of compounds.
- Melendez Gomez, Carlos M.,Kouznetsov, Vladimir V.,Sortino, Maximiliano A.,Alvarez, Sandra L.,Zacchino, Susana A.
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experimental part
p. 7908 - 7920
(2009/04/11)
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- A Novel Approach to 2-Arylated Quinolines: Electrocyclization of Alkynyl Imines via Vinylidene Complexes
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(Matrix presented) Alkynyl imines underwent [4 + 2] electrocyclization in the presence of 20 mol % W(CO)5(THF) to give 2-arylated quinolines in good yields. A deuterium labeling study suggests that the reaction proceeds via a tungsten vinylidene complex.
- Sangu, Kenichiro,Fuchibe, Kohei,Akiyama, Takahiko
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p. 353 - 355
(2007/10/03)
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- A simple and new synthetic method for the preparation of 2-phenyl-6-substituted quinolines
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2-phenylquinoline derivatives have been synthesized through the thermolysis of suitable enaminoimine hydrochlorides.
- Roy,Kar,Ray
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p. 1959 - 1965
(2007/10/02)
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- Mechanism of the Skraup and Doebner-von Miller Quinoline Syntheses: Cyclization of α,β-Unsaturated N-Aryliminium Salts via 1,3-Diazetidinium Ion Intermediates
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The hydrochlorides of cinnamaldehyde anils of the type ArCH=CHCH=NAr', where Ar and Ar' are phenyl or p-tolyl groups, have been shown to react between 25 deg C and 100 deg C, in a toluene suspension or in a solution of DMSO or acetonitrile, to yield 2-substituted quinolines and N-cinnamylanilines ArCH=CHCH2NHAr'.The reaction proceeds under anhydrous conditions by cyclization of the anil hydrochlorides themselves to produce ultimately 2-substituted quinolines.The kinetics of the reaction follow a first-order dependence on the anil hydrochloride.Rapid exchange occurring between dissimilar anil hydrochlorides suggests that such anil metatheses take place by way of 1,3-diazetidinium ion intermediates, which previous studies have shown would possess the requisite metastability.The foregoing experimental observations are reconciled in terms of a novel mechanism for the formation of quinolines directly from anils under acidic conditions, namely, the reversible formation of diazetidinium ions and their irreversible cyclization to quinolines.It is proposed that this pathway is the operative mechanism in the classic Skraup and Doebner-von Miller quinoline syntheses.
- Eisch, John J.,Dluzniewski, Tomasz
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p. 1269 - 1274
(2007/10/02)
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