- Asymmetric Synthesis of Hydroquinolines with α,α-Disubstitution through Organocatalyzed Kinetic Resolution
-
The first kinetic resolution of hydroquinoline derivatives with α,α-disubstitution has been achieved through asymmetric remote aminations with azodicarboxylates enabled by chiral phosphoric acid catalysis. Mechanistic studies suggest a monomeric catalyst pathway proceeding through rate- and enantio-determining electrophilic attack promoted by a network of attractive non-covalent interactions between the substrate and catalyst. Facile subsequent removal and transformations of the newly introduced hydrazine moiety enable these protocols to serve as powerful tools for asymmetric synthesis of N-heterocycles with α,α-disubstitution.
- Chen, Yunrong,Zhu, Chaofan,Guo, Zheng,Liu, Wei,Yang, Xiaoyu
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supporting information
p. 5268 - 5272
(2021/02/05)
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- Kinetic Resolution of 2,2-Disubstituted Dihydroquinolines through Chiral Phosphoric Acid-Catalyzed C6-Selective Asymmetric Halogenations
-
A novel kinetic resolution of 2,2-disubstituted dihydroquinolines was achieved by regioselective asymmetric halogenations enabled by chiral phosphoric acid catalysis. A series of dihydroquinolines bearing 2,2-disubstitutions were well-tolerated in these reactions, generating both the recovered dihydroquinolines and C-6-brominated products with high enantioselectivities, with s-factors up to 149. In addition, this kinetic resolution protocol is also applicable for 2,2-disubstituted tetrahydroquinoline and asymmetric iodonation reaction.
- Chen, Yunrong,He, Yu-Peng,Liu, Wei,Tao, Houchao,Yang, Xiaoyu,Zhao, Fei,Zhu, Chaofan
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supporting information
p. 4104 - 4108
(2021/06/27)
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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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- Visible-Light-Mediated Oxidative Cyclization of 2-Aminobenzyl Alcohols and Secondary Alcohols Enabled by an Organic Photocatalyst
-
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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- 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; 0117-0118
(2021/01/24)
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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
- -
-
Paragraph 0011; 0040
(2022/01/10)
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- The preparation of a Co@C3N4catalyst and applications in the synthesis of quinolines from 2-aminobenzyl alcohols with ketones
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An unsymmetrical diphenylphosphino-pyridinyl-triazole ligand was synthesized and characterized through IR, NMR and MS and the corresponding earth-abundant metal complex (cobalt) was prepared. Considering energy consumption and environmental friendliness, it is necessary to turn this diphenylphosphino-pyridinyl-triazole cobalt complex into a recyclable catalyst, which could easily be reused. Therefore, a heterogeneous catalyst was synthesized through Co-doping of C3N4, and the Co-nanoparticles on C3N4revealed high catalytic activity for the synthesis of quinolines with good recovery performance.
- Cao, Fei,Mao, Anruo,Yang, Bobin,Ge, Chenyang,Wang, Dawei
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supporting information
p. 6768 - 6772
(2021/04/22)
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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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-
- Preparation of 2-Arylquinolines from 2-Arylethyl Bromides and Aromatic Nitriles with Magnesium and N -Iodosuccinimide
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Treatment of 2-arylethylmagnesium bromides, prepared from 2-arylethyl bromides and magnesium, with aromatic nitriles, followed by reaction with water and then with N -iodosuccinimide under irradiation with a tungsten lamp, gave the corresponding 2-arylquinolines in good to moderate yields under transition-metal-free conditions. 2-Alkylquinolines could be also obtained in moderate yields by the same procedure with 2-arylethyl bromides, magnesium, aliphatic nitriles bearing a secondary alkyl group, and N -iodosuccinimide.
- Naruto, Hiroki,Togo, Hideo
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p. 1122 - 1130
(2020/04/01)
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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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- 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.
- -
-
Paragraph 0020; 0034-0035
(2020/08/09)
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- Half-Sandwich Ruthenium Complexes for One-Pot Synthesis of Quinolines and Tetrahydroquinolines: Diverse Catalytic Activity in the Coupled Cyclization and Hydrogenation Process
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Four types of half-sandwich ruthenium complexes with an N,O-coordinate mode based on hydroxyindanone-imine ligands have been prepared in good yields. These stable ruthenium complexes exhibited high activity in the catalytic synthesis of quinolines from the reactions of amino alcohols with different types of ketones or secondary alcohols under very mild conditions. Moreover, the methodology for the direct one-pot synthesis of tetrahydroquinoline derivatives from amino alcohols and ketones has been also developed on the basis of the continuous catalytic activity of this ruthenium catalyst in the selective hydrogenation of the obtained quinoline derivatives with a low catalyst loading. The corresponding products, quinolines and tetrahydroquinoline derivatives, were afforded in good to excellent yields. The efficient and diverse catalytic activity of these ruthenium complexes suggested their potential large-scale application. All of the ruthenium complexes were characterized by various spectroscopies to confirm their structures.
- Yun, Xue-Jing,Zhu, Jing-Wei,Jin, Yan,Deng, Wei,Yao, Zi-Jian
-
supporting information
p. 7841 - 7851
(2020/06/04)
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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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- Synergy of anodic oxidation and cathodic reduction leads to electrochemical deoxygenative C2 arylation of quinoline: N-oxides
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The first example of electrochemical deoxygenative C2 arylation of quinoline N-oxides using sulfonyl hydrazines was demonstrated in this work. By employing both anodic oxidation and cathodic reduction, a variety of 2-arylquinolines were synthesized under metal catalyst-, exogenous-oxidant-, and exogenous-reductant-free conditions.
- Yuan, Yong,Jiang, Minbao,Wang, Tao,Xiong, Yunkui,Li, Jun,Guo, Huijiao,Lei, Aiwen
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p. 11091 - 11094
(2019/09/20)
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- Iridium-Mediated Arylation of Quinoline via the Cleavage of Carbon-Carbon and Carbon-Nitrogen Bonds of 1,3-Dimesitylimidazol-2-ylidene
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The iridium-mediated direct arylation of quinoline using an NHC ligand is reported. This reaction proceeds via cleavage of the carbon-carbon and carbon-nitrogen bonds of the NHC ligand and a carbon-hydrogen bond of quinoline.
- Sakurai, Shun,Tobisu, Mamoru
-
supporting information
p. 2834 - 2838
(2019/08/15)
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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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- Reaction condition controlled nickel(ii)-catalyzed C-C cross-coupling of alcohols
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The challenge in the C-C cross-coupling of secondary and primary alcohols using acceptorless dehydrogenation coupling (ADC) is the difficulty in accurately controlling product selectivities. Herein, we report a controlled approach to a diverse range of β-alkylated secondary alcohols, α-alkylated ketones and α,β-unsaturated ketones using the ADC methodology employing a Ni(ii) 4,6-dimethylpyrimidine-2-thiolate cluster catalyst under different reaction conditions. This catalyst could tolerate a wide range of substrates and exhibited a high activity for the annulation reaction of secondary alcohols with 2-aminobenzyl alcohols to yield quinolines. This work is an example of precise chemoselectivity control by careful choice of reaction conditions.
- Zhang, Meng-Juan,Li, Hong-Xi,Young, David J.,Li, Hai-Yan,Lang, Jian-Ping
-
supporting information
p. 3567 - 3574
(2019/04/14)
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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
-
supporting information
p. 16099 - 16105
(2019/11/26)
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- Manganese(I)-Catalyzed Transfer Hydrogenation and Acceptorless Dehydrogenative Condensation: Promotional Influence of the Uncoordinated N-Heterocycle
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The four bidentate manganese(I) complexes [(C5H4N-C5H3N-OH)Mn(CO)3Br] (1), [(C9H6N-C5H3N-OH)Mn(CO)3Br] (2), [(C8H5N2-C5H3N-OH)Mn(CO)3Br] (3), and [(C8H5N2-C5H3N-OCH3)Mn(CO)3Br] (4) were synthesized. These complexes were tested as catalysts for the transfer hydrogenation of ketones, and 3 showed the highest activity. The reactions proceeded well with 0.5 mol % of catalyst loading and 20 mol % of t-BuOK at 85 °C for 24 h. Furthermore, 3 was also used as a catalyst for the synthesis of primary alcohols via transfer hydrogenation of aldehydes and the synthesis of 1,2-disubstituted benzimidazoles and quinolines via acceptorless dehydrogenative condensations.
- Zhang, Chong,Hu, Bowen,Chen, Dafa,Xia, Haiping
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p. 3218 - 3226
(2019/09/13)
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- Quinoline derivative synthesis method
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The invention discloses a quinoline derivative synthesis method. The method comprises the steps that substitutional acetophenone, aniline and dimethyl sulfoxide perform one-pot reaction in an oxygen-containing atmosphere in the presence of a copper salt catalyst to obtain a quinoline derivative. The quinoline derivative types are enriched and more intermediates are provided for drug synthesis by adopting the method, raw materials are wide in source, the steps are simple, reaction conditions are mild, the yield is high, and the method facilitates industrial production.
- -
-
Paragraph 0041; 0043; 0097-0101
(2018/04/21)
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- Method for intermolecular cyclization synthesis of quinoline derivative
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The invention discloses a method for intermolecular cyclization synthesis of a quinoline derivative. The method comprises the following step: in an atmosphere of oxygen, performing a one-pot reactionon aryl aceton, phenylamine and dimethyl sulfoxide in the presence of a ferric salt and/or ferrite catalyst, thereby obtaining the quinoline derivative. By adopting the method, the types of quinolinederivatives are enriched, a relatively large amount of intermittent are provided for medicine synthesis, and in addition, the method is wide in raw material source, simple in step, gentle in reactioncondition, high in yield and beneficial to industrial production.
- -
-
Paragraph 0042; 0098-0102
(2018/03/25)
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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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- 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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- 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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- 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.
- -
-
Paragraph 0033; 0034
(2016/10/09)
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- Visible light-induced aerobic C-N bond activation: A photocatalytic strategy for the preparation of 2-arylpyridines and 2-arylquinolines
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An efficient method for accessing arylpyridines and arylquinolines via visible light-induced aerobic C-N bond activation is described. The applicability of different kinds of simple ketones, easily available amines, and the use of air as the sole oxidant make this transformation very attractive.
- Hu, Bei,Li, Yuyuan,Dong, Wuheng,Xie, Xiaomin,Wan, Jun,Zhang, Zhaoguo
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p. 48315 - 48318
(2016/06/09)
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- Synthesis of 2-substituted quinolines from alcohols
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A facile and economic method for the construction of 2-substituted quinolines by AgOTf-catalyzed 2-aminobenzyl alcohol and alkyne/ketone or 2-aminophenethyl alcohol and aldehyde has been developed. The electronic properties of the substituents on the alkyne, ketone, and aldehyde 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. Moreover, the use of inexpensive starting materials and environmentally benign oxidants makes this atom efficient method particularly attractive.
- Xu, Xuefeng,Zhang, Xu,Liu, Wenming,Zhao, Qiang,Wang, Zhiqiang,Yu, Lintao,Shi, Fu
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supporting information
p. 3790 - 3792
(2015/06/08)
-
- 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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- 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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- Lithium tert-butoxide mediated α-alkylation of ketones with primary alcohols under transition-metal-free conditions
-
LiOtBu was found to efficiently promote the α-alkylation reaction of ketones with primary alcohols, without the addition of any transition metal catalyst.
- Liang, Yu-Feng,Zhou, Xin-Feng,Tang, Shi-Ya,Huang, Yao-Bing,Feng, Yi-Si,Xu, Hua-Jian
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p. 7739 - 7742
(2013/06/27)
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- Pd-catalyzed cross-coupling of aryl carboxylic acids with propiophenones through a combination of decarboxylation and dehydrogenation
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A palladium-catalyzed cross-coupling reaction of aryl carboxylic acids with saturated propiophenones through a combination of decarboxylation and dehydrogenation to form Heck-type products was reported. In a glove box, a 25 mL tube equipped with a stir bar was charged with Pd(OAc)2, PCy3, propiophenone, 2-nitrobenzoic acid, Ag2CO3 and nBu4NOAc HOAc. Then, the mixture was heated under nitrogen at 90°C in DMF for 24 h. After cooling down, the crude reaction mixture was analyzed by GC with n-dodecane as an internal standard to obtain 3a in 75% GC yield. Relatively weak bases, such as carboxylate salts, facilitated this reaction and the effect of the bases was a function of their solubility, while strong bases, such as K3PO4 and K2CO3 shut down the reaction completely. The simultaneous use of carboxylate salts and equimolar carboxylic acids significantly improved the yield of 3a, although the use of acetic acid alone was ineffective for the reaction.
- Zhou, Jun,Wu, Ge,Zhang, Min,Jie, Xiaoming,Su, Weiping
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supporting information; experimental part
p. 8032 - 8036
(2012/08/13)
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- Base-mediated synthesis of quinolines: an unexpected cyclization reaction between 2-aminobenzylalcohol and ketones
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Quinolines are prepared in an oxidative cyclization reaction between 2-aminobenzylalcohol and ketones. This reaction, that involves a hydrogen transfer, is mediated solely by a base without the need for a transition metal catalyst.
- Mierde, Hans Vander,Voort, Pascal Van Der,Verpoort, Francis
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body text
p. 6893 - 6895
(2009/04/10)
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- A ruthenium-catalyzed approach to the friedlaender quinoline synthesis
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In a modification of the Friedlaender reaction, 2-aminobenzyl alcohol is oxidatively cyclized with a variety of ketones to yield substituted quinolines. Of all the ruthenium catalysts that were tested for this reaction, the second-generation Grubbs' catalyst gives the highest quinoline yield, in combination with KOtBu as a base. The presence of a hydrogen acceptor is required to regenerate the catalyst. Also the reaction mechanism is discussed, and the results show that there are possibly two different pathways towards quinolines. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Mierde, Hans Vander,Van Der Voort, Pascal,De Vos, Dirk,Verpoort, Francis
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scheme or table
p. 1625 - 1631
(2009/04/11)
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- A recyclable palladium-catalyzed modified Friedl?nder quinoline synthesis
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2-Aminobenzyl alcohol reacts with an array of ketones in toluene/poly(ethylene glycol) (PEG-2000) at 100 °C in the presence of a palladium catalyst along with KOH under an atmosphere of air to give the corresponding quinolines in good yields. The catalytic system could be recovered and reused five times without any loss of catalytic activity.
- Cho, Chan Sik,Ren, Wen Xiu
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p. 4182 - 4186
(2008/02/10)
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- Improved ruthenium catalysts for the modified Friedlaender quinoline synthesis
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Herein we describe an improved ruthenium catalyst for the oxidative cyclization of 2-aminobenzylalcohol with ketones, leading to quinolines via a modified Friedlaender synthesis. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
- Vander Mierde, Hans,Ledoux, Nele,Allaert, Bart,Van Der Voort, Pascal,Drozdzak, Renata,De Vos, Dirk,Verpoort, Francis
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p. 1572 - 1574
(2008/03/13)
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- A copper(II)-catalyzed protocol for modified Friedl?nder quinoline synthesis
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2-Aminobenzyl alcohol reacts with an array of ketones in dioxane at 100 °C in the presence of a catalytic amount of CuCl2 along with KOH under O2 atmosphere to afford the corresponding quinolines in good yields. 2-Aminobenzyl alcohol is also oxidatively coupled and cyclized with various aldehydes by step-by-step procedure, an initial treatment of 2-aminobenzyl alcohol in the presence of CuCl2 and KOH in dioxane under O2 atmosphere and subsequent addition of aldehyde to the mixture followed by stirring under argon atmosphere, to give 3-substituted quinolines in moderate to good yields.
- Cho, Chan Sik,Ren, Wen Xiu,Shim, Sang Chul
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p. 6781 - 6785
(2007/10/03)
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- Palladium-catalyzed Sonogashira coupling reaction followed by isomerization and cyclization
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2-Iodoaniline reacts with terminal acetylenic carbinols in THF at 80 °C in the presence of a catalytic amount of PdCl2(PPh3) 2 and CuI along with aqueous tetrabutylammonium hydroxide to afford the corresponding 2-arylquinolines in good yields. The catalytic pathway seems to be proceeded via a sequence involving initial Sonogashira coupling between 2-iodoaniline and terminal acetylenic carbinols to form coupled acetylenic carbinols, isomerization of coupled acetylenic carbinols to α,β- unsaturated ketones, and cyclodehydration.
- Cho, Chan Sik
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p. 4094 - 4097
(2007/10/03)
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- A rhodium-catalyzed route for oxidative coupling and cyclization of 2-aminobenzyl alcohol with ketones leading to quinolines
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2-Aminobenzyl alcohol undergoes oxidative cyclization with aryl(alkyl), alkyl(alkyl) and cyclic ketones in dioxane at 80° in the presence of a catalytic amount of RhCl(PPh3)3 along with KOH to afford the corresponding quinolines in good yields. The catalytic pathway seems to be proceeded via a sequence involving initial oxidation of 2-aminobenzyl alcohol to 2-aminobenzaldehyde by a rhodium catalyst, cross aldol reaction between 2-aminobenzaldehyde and ketones, and cyclodehydration.
- Cho, Chan Sik,Seok, Hyo Jin,Shim, Sang Chul
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p. 1219 - 1222
(2007/10/03)
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- Consecutive isomerization and cyclization of 3-(2-Aminophenyl)-1-arylprop- 2-yn-1-ols leading to 2-arylquinolines in the presence of potassium hydroxide
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3-(2-Aminophenyl)-1-arylprop-2-yn-1-ols are readily converted to 2-arylquinolines in good yields in ethanol at 80° in the presence of potassium hydroxide via domino isomerization and cyclization.
- Cho, Chan Sik,Lee, Na Young,Kim, Tae-Jeong,Shim, Sang Chul
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p. 409 - 411
(2007/10/03)
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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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- Multifunctional catalysis of a ruthenium-grafted hydrotalcite: One-pot synthesis of quinolines from 2-aminobenzyl alcohol and various carbonyl compounds via aerobic oxidation and aldol reaction
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The Ru-grafted hydrotalcite was found to be an excellent multifunctional catalyst for one-pot synthesis of quinolines from 2-aminobenzyl alcohol and various carbonyl compounds. These quinolines were obtained through aerobic oxidation by the Ru species, followed by aldol reaction on base sites of the hydrotalcite.
- Motokura, Ken,Mizugaki, Tomoo,Ebitani, Kohki,Kaneda, Kiyotomi
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p. 6029 - 6032
(2007/10/03)
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- Ruthenium-catalyzed oxidative coupling and cyclization between 2-aminobenzyl alcohol and secondary alcohols leading to quinolines
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2-Aminobenzyl alcohol is oxidatively coupled and cyclized with secondary alcohols in dioxane at 80°C in the presence of a catalytic amount of RuCl2(PPh3)3 and KOH along with 1-dodecene as a sacrificial hydrogen acceptor to give the corresponding quinolines in good yields. The cyclization is applicable to a wide range of alkyl(aryl) and alkyl(alkyl) carbinols. The catalytic pathway seems to be proceeded via a sequence involving initial oxidation of both substrates to carbonyl compounds, cross aldol reaction, and cyclodehydration.
- Cho, Chan Sik,Kim, Bok Tae,Choi, Heung-Jin,Kim, Tae-Jeong,Shim, Sang Chul
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p. 7997 - 8002
(2007/10/03)
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- Ruthenium-catalysed oxidative cyclisation of 2-aminobenzyl alcohol with ketones: modified Friedlaender quinoline synthesis
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2-Aminobenzyl alcohol is oxidatively cyclised with an array of ketones in dioxane at 80 deg C in the presence of a catalytic amount of a ruthenium catalyst and KOH to afford the corresponding quinolines in high yields.
- Cho, Chan Sik,Kim, Bok Tae,Kim, Tae-Jeong,Shim, Sang Chul
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p. 2576 - 2577
(2007/10/03)
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- The palladium-catalyzed transfer hydrogenation/heterocyclization of β- (2-aminophenyl)-α,β-ynones. An approach to 2-aryl- and 2-vinylquinolines
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The palladium-catalyzed transfer hydrogenation/cyclization of readily available β-(o-aminophenyl)-α,β-ynones I affords 2-aryl- and 2- vinylquinolines 3 in good yield.
- Cacchi, Sandro,Fabrizi, Giancarlo,Marinelli, Fabio
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p. 401 - 404
(2007/10/03)
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- Palladium-catalyzed heteroannulation with acetylenic carbinols as synthons-synthesis of quinolines and 2,3-dihydro-4(1H)-quinolones
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o-Iodoanilides 4 reacted with terminal acetylenic carbinols 5 under palladium-catalyzed conditions to yield o-substituted anilides 6. Most of the anilides 6 could be cyclized with NaOEt/EtOH to 2-arylquinolines 2. o-Iodoanilines 7 reacted with carbinols 5 leading to 8 which on palladium(II) assisted cyclisation afforded substituted quinolines 2. An excellent synthesis of the alkaloid dubamine (2n) is reported. Also, the anilides 6 on acid-catalyzed rearrangement, deprotection and cyclisation led to the 2-aryl-2, 3-dihydro-4(1H)-quinolones 16.
- Mahanty, Jyan S.,De, Mahuya,Das, Palas,Kundu, Nitya G.
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p. 13397 - 13418
(2007/10/03)
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- Synthesis of Quinolines and 2,3-Dihydro-4(1H)-quinolones. Palladium Catalysed Reaction of o-Iodoanilides with Acetylenic Carbinols
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A facile and general synthesis of quinolines and 2,3-dihydro-4(1H)-quinolones was accomplished through palladium catalysed reaction of o-iodoanilides with acetylenic carbinols.Key Words: quinolines; 2,3-dihydro-4(1H)-quinolones; palladium catalysis; o-iodoanilines; acetylenic carbinols.
- Kundu, Nitya G.,Mahanty, Jyan S.,Das, Palas,Das, Biswajit
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p. 1625 - 1628
(2007/10/02)
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