- A Mild and Efficient One-Step Synthesis of Quinolines
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(Equation presented) The Friedlaender synthesis of quinolines is an extensively employed protocol, yielding the desired heterocycle in a two-step reduction-condensation sequence. We have developed a mild, efficient, high-yielding single-step variant of this methodology, which employs SnCl 2 and ZnCl2 to effect the reaction.
- McNaughton, Brian R.,Miller, Benjamin L.
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- Oxygen-implanted MoS2 nanosheets promoting quinoline synthesis from nitroarenes and aliphatic alcohols via an integrated oxidation transfer hydrogenation-cyclization mechanism
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We herein report that MoS2 with oxygen-implanting modification (O-MoS2) can work as a multifunctional catalyst to achieve the one-pot quinoline synthesis from basic nitroarenes and aliphatic alcohols. Different from common knowledge that the application of MoS2-based catalysts and above quinoline synthesis need anaerobic conditions, we conduct the heterogeneous catalysis under an unusual air atmosphere. Catalyst characterization and experimental results indicate that the MoOx clusters implanted in the MoS2 skeleton, not the coordinatively unsaturated Mo sites (CUS Mo), dominate the generation of quinolines. By overturning the catalysis perception that O2 adsorption on MoSx can deactivate the MoS2-based catalysts using an efficient method for in situ healing of the MoOx structure in O-MoS2 and protecting the O-MoS2 catalyst by inhibiting unwanted MoOx elimination with extra H*, we innovatively introduce O2 into the quinoline synthesis. The robust O-MoS2 can be consecutively used ten times without regeneration and it offers 69-75% yields of 2-methylquinoline from nitrobenzene and ethanol. Furthermore, different from the traditional transfer hydrogenation-condensation mechanism, an integrated oxidation-transfer hydrogenation-cyclization mechanism is proposed over the O-MoS2 catalyst.
- Gao, Zhuyan,Huang, Zhipeng,Lu, Jianmin,Mu, Junju,Ren, Puning,Su, Kaiyi,Wang, Feng,Zhang, Chaofeng,Zhang, Shichao
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p. 1704 - 1713
(2022/03/08)
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- Dilithium Amides as a Modular Bis-Anionic Ligand Platform for Iron-Catalyzed Cross-Coupling
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Dilithium amides have been developed as a bespoke and general ligand for iron-catalyzed Kumada-Tamao-Corriu cross-coupling reactions, their design taking inspiration from previous mechanistic and structural studies. They allow for the cross-coupling of alkyl Grignard reagents with sp2-hybridized electrophiles as well as aryl Grignard reagents with sp3-hybridized electrophiles. This represents a rare example of a single iron-catalyzed system effective across diverse coupling reactions without significant modification of the catalytic protocol, as well as remaining operationally simple.
- Neate, Peter G.N.,Zhang, Bufan,Conforti, Jessica,Brennessel, William W.,Neidig, Michael L.
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supporting information
p. 5958 - 5963
(2021/08/18)
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- SULFONYL-SUBSTITUTED BICYCLIC COMPOUND WHICH ACTS AS ROR INHIBITOR
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Provided is a sulfonyl-substituted bicyclic compound (A) which acts as a RORγ inhibitor, said compound has good RORγ inhibitory activity and is expected to be used for treating diseases mediated by a RORγ receptor in mammals.
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Paragraph 0342; 0344
(2020/08/16)
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- ZnMe2-Mediated, Direct Alkylation of Electron-Deficient N-Heteroarenes with 1,1-Diborylalkanes: Scope and Mechanism
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The regioselective, direct alkylation of electron-deficient N-heteroarenes is, in principle, a powerful and efficient way of accessing alkylated N-heteroarenes that are important core structures of many biologically active compounds and pharmaceutical agents. Herein, we report a ZnMe2-promoted, direct C2- or C4-selective primary and secondary alkylation of pyridines and quinolines using 1,1-diborylalkanes as alkylation sources. While substituted pyridines and quinolines exclusively afford C2-alkylated products, simple pyridine delivers C4-alkylated pyridine with excellent regioselectivity. The reaction scope is remarkably broad, and a range of C2- or C4-alkylated electron-deficient N-heteroarenes are obtained in good yields. Experimental and computational mechanistic studies imply that ZnMe2 serves not only as an activator of 1,1-diborylalkanes to generate (α-borylalkyl)methylalkoxy zincate, which acts as a Lewis acid to bind to the nitrogen atom of the heterocycles and controls the regioselectivity, but also as an oxidant for rearomatizing the dihydro-N-heteroarene intermediates to release the product.
- Jo, Woohyun,Baek, Seung-Yeol,Hwang, Chiwon,Heo, Joon,Baik, Mu-Hyun,Cho, Seung Hwan
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supporting information
p. 13235 - 13245
(2020/09/01)
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- Method for preparing quinoline derivative
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The invention relates to a method for preparing a quinoline derivative. The method comprises the following steps: by taking aromatic amine compounds and fatty alcohol as raw materials and oxygen-containing molybdenum disulfide as a catalyst, performing a reaction for 2-12 hours in an inert atmosphere or an oxygen-containing atmosphere at the temperature of 120-200 DEG C, after the reaction is finished, separating liquid phase components, performing concentration, and performing separation through a silica gel column, so as to obtain a substituted quinoline compound. The synthetic method may have important application in the aspect of quinoline compound synthesis.
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Paragraph 0043-0044
(2020/02/17)
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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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- Highly Diastereo- And Enantioselective Ir-Catalyzed Hydrogenation of 2,3-Disubstituted Quinolines with Structurally Fine-Tuned Phosphine-Phosphoramidite Ligands
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A highly diastereo- and enantioselective Ir-catalyzed hydrogenation of unfunctionalized 2,3-disubstituted quinolines, especially 3-alkyl-2-arylquinolines, has been realized. The success of this hydrogenation is ascribed to the use of a structurally fine-tuned chiral phosphine-phosphoramidite ligand with a (Sa)-3,3′-dimethyl H8-naphthyl moiety and (Rc)-1-phenylethylamine backbone. The hydrogenation displayed broad functional group tolerance, thus furnishing a wide range of optically active 2,3-disubstituted tetrahydroquinolines in up to 96% ee and with perfect cis-diastereoselectivity.
- Hu, Xin-Hu,Hu, Xiang-Ping
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supporting information
p. 10003 - 10006
(2019/12/24)
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- Pd-Catalyzed Alkylation of (Iso)quinolines and Arenes: 2-Acylpyridine Compounds as Alkylation Reagents
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The first Pd-catalyzed alkylation of (iso)quinolines and arenes is reported. The readily available and bench-stable 2-acylpyridine compounds were used as an alkylation reagent to form the structurally versatile alkylated (iso)quinolines and arenes. The method affords a convenient pathway for the introduction of alkyl groups into organic molecules.
- Wu, Qingsong,Han, Shuaijun,Ren, Xiaoxiao,Lu, Hongtao,Li, Jingya,Zou, Dapeng,Wu, Yangjie,Wu, Yusheng
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supporting information
p. 6345 - 6348
(2018/10/20)
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- Deracemization of Phenyl-Substituted 2-Methyl-1,2,3,4-Tetrahydroquinolines by a Recombinant Monoamine Oxidase from Pseudomonas monteilii ZMU-T01
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A monoamine oxidase (MAO5) from Pseudomonas monteilii ZMU-T01 was first heterologously expressed in Escherichia coli BL21(DE3) and then used as a biocatalyst for the deracemization of racemic 2-methyl-1,2,3,4-tetrahdroquinoline derivatives to yield the unreacted R enantiomer with up to >99 % ee. Sequence alignment revealed that MAO5 shared 14.7 % identity toward the well-studied monoamine oxidase (MAO-N).
- Deng, Guozhong,Wan, Nanwei,Qin, Lei,Cui, Baodong,An, Miao,Han, Wenyong,Chen, Yongzheng
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p. 2374 - 2377
(2018/04/19)
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- Efficient and versatile catalysis for β-alkylation of secondary alcohols through hydrogen auto transfer process with newly designed ruthenium(II) complexes containing ON donor aldazine ligands
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A new series of ruthenium(II) carbonyl complexes, [RuCl(CO)(EPh3)2(L1-2)] (1–4) (E?=?P or As; H2L1?=?salicylaldazine, H2L2?=?2-hydroxynaphthaldazine), have been assembled from ruthenium(II) precursors [RuHCl(CO)(EPh3)3] and bidentate ON donor Schiff base ligands (H2L1-2). Both ligands and their new ruthenium(II) complexes have been characterized by elemental analyses, spectroscopic methods (UV, IR, NMR (1H, 13C, 31P) as well as ESI mass spectrometry. The molecular structures of H2L1 and 1 have been confirmed by single crystal X-ray diffraction. Based on the above studies, an octahedral coordination geometry around the metal center has been proposed for 1–4. To investigate the catalytic effectiveness of 1–4, the complexes have been used as catalysts in β-alkylation of secondary alcohols with primary alcohols and synthesis of quinolines. The effect of solvent, time, base, catalyst loading, and substituent of the ligand moiety on the reaction was studied. Notably, 1 was a more efficient catalyst toward alkylation of a wide range of alcohols and quinolines synthesis. The reusability of the catalyst was checked and the results showed up to six catalytic runs without significant loss of activity.
- Premkumar, Periyasamy,Manikandan, Rajendran,Nirmala, Muthukumaran,Viswanathamurthi, Periasamy,Malecki, Jan Grzegorz
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p. 3065 - 3079
(2017/10/11)
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- Synthesis of 2-Substituted Quinolines via Rhodium(III)-Catalyzed C–H Activation of Imidamides and Coupling with Cyclopropanols
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An efficient synthesis of 2-substituted quinolines from readily available cyclopropanols and imidamides has been developed, where the cyclopropanol acts as a C3 synthon. With the assistance of a bifunctional imidamide directing group, the reaction occurred via sequential C–H/C–C cleavage and C–C/C–N bond formation. (Figure presented.).
- Zhou, Xukai,Qi, Zisong,Yu, Songjie,Kong, Lingheng,Li, Yang,Tian, Wan-Fa,Li, Xingwei
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p. 1620 - 1625
(2017/05/22)
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- Traceless Directing-Group Strategy in the Ru-Catalyzed, Formal [3 + 3] Annulation of Anilines with Allyl Alcohols: A One-Pot, Domino Approach for the Synthesis of Quinolines
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A unique, ruthenium-catalyzed, [3 + 3] annulation of anilines with allyl alcohols in the synthesis of substituted quinolines is reported. The method employs a traceless directing group strategy in the proximal C-H bond activation and represents a one-pot Domino synthesis of quinolines from anilines.
- Kumar, Gangam Srikanth,Kumar, Pravin,Kapur, Manmohan
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supporting information
p. 2494 - 2497
(2017/05/24)
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- Chromium-Catalyzed Cross-Coupling Reactions of Alkylmagnesium Reagents with Halo-Quinolines and Activated Aryl Chlorides
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An efficient protocol for chromium(III)-catalyzed C(sp2)-C(sp3) cross-coupling is reported. The alkylations of halo-quinoline and phenacyl derivatives proceed at room temperature within minutes using the tetrahydrofuran-soluble chrom
- Bellan, Andreas B.,Kuzmina, Olesya M.,Vetsova, Violeta A.,Knochel, Paul
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p. 188 - 194
(2016/12/24)
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- Transition-Metal-Free Regioselective Alkylation of Pyridine N-Oxides Using 1,1-Diborylalkanes as Alkylating Reagents
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Reported herein is an unprecedented base-promoted deborylative alkylation of pyridine N-oxides using 1,1-diborylalkanes as alkyl sources. The reaction proceeds efficiently for a wide range of pyridine N-oxides and 1,1-diborylalkanes with excellent regioselectivity. The utility of the developed method is demonstrated by the sequential C?H arylation and methylation of pyridine N-oxides. The reaction also can be applied for the direct introduction of a methyl group to 9-O-methylquinine N-oxide, thus it can serve as a powerful method for late-stage functionalization.
- Jo, Woohyun,Kim, Junghoon,Choi, Seoyoung,Cho, Seung Hwan
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supporting information
p. 9690 - 9694
(2016/08/10)
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- Bio-mediated oxidative resolution of racemic 2-substituted 1,2,3,4-tetrahydroquinolines
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Whole cell of Pseudomonas monteilii ZMU-T01 strains mediated oxidative resolution of racemic 2-substituted 1,2,3,4-tetrahydroquinolines has been successfully described. A series of highly enantioselective 2-substituted 1,2,3,4-tetrahydroquinoline derivatives were obtained in up to 50% conversion and >99% ee.
- Qin, Lei,Zheng, Daijun,Cui, Baodong,Wan, Nanwei,Zhou, Xiaojian,Chen, Yongzheng
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supporting information
p. 2403 - 2405
(2016/05/19)
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- Direct alkenylation of alkylazaarenes with aldehydes through C(sp3)-H functionalization under catalytic InCl3 activation
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Under the influence of InCl3 as a Lewis acid catalyst, a methodology on the C(sp3)-H functionalization of alkylazaarenes has been demonstrated through the activation of benzylic C-H bonds towards their addition reaction with the appropriate electrophiles. This methodology was chiefly applied in the direct alkenylation of primary and secondary benzylic C-H bonds of alkylazaarenes with aldehydes. A variety of alkenyl products were afforded in generally good yields including the starting alkenyl intermediate used in the synthesis of montelukast and other related molecules.
- Jamal, Zaini,Teo, Yong-Chua,Lim, Gina Shiyun
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p. 2132 - 2138
(2016/04/19)
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- A general method for N-methylation of amines and nitro compounds with dimethylsulfoxide
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DMSO methylates a broad range of amines in the presence of formic acid, providing a novel, green and practical method for amine methylation. The protocol also allows the one-pot transformation of aromatic nitro compounds into dimethylated amines in the presence of a simple iron catalyst. Not just a solvent: DMSO methylates a broad range of amines in the presence of formic acid, providing a novel, green and practical method for amine methylation. The protocol also allows the one-pot transformation of aromatic nitro compounds into dimethylated amines in the presence of a simple iron catalyst. Copyright
- Jiang, Xue,Wang, Chao,Wei, Yawen,Xue, Dong,Liu, Zhaotie,Xiao, Jianliang
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supporting information
p. 58 - 63
(2014/01/17)
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- ANTI-ANGIOGENIC COMPOUNDS
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(E)-2-(2-Quinolin-2-yl-propenyl)-phenol, 2-Quinolin-2-yl-ylethynyl-phenol and salts thereof are useful as medicaments, especially for treatment of an angiogenesis-related disease or disorder.
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Page/Page column 38
(2014/02/15)
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- Functionalization of the Benzylic C-H Bonds in Azaarenes by Cobalt-Catalyzed 1,4-Addition to Enones
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Functionalization of the C(sp3)-H bonds in azaarenes was catalyzed by CoCl2 as an inexpensive Lewis acid catalyst. Enones were demonstrated to be good C=C electrophilic acceptors for the construction of various azaarene-containing 1,4-addition products in yields of up to 95 %. Functionalization of the C(sp3)-H bonds in azaarenes catalyzed by CoCl2 as an inexpensive Lewis acid catalyst is reported. Enones are demonstrated to be good C=C electrophilic acceptors for the construction of various azaarene-containing 1,4-addition products in yields up to 95 %.
- Jamal, Zaini,Teo, Yong-Chua,Wong, Ling-Keong
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supporting information
p. 7343 - 7346
(2016/02/20)
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- An unexpected one-pot synthesis of multi-substituted quinolines via a cascade reaction of Michael/Staudinger/aza-Wittig/aromatization of ortho-azido-β-nitro-styrenes with various carbonyl compounds
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Multi-substituted quinolines 3 were unexpectedly prepared from a cascade reaction of ortho-azido-β-nitro-styrenes with various carbonyl compounds. This method takes advantages of mild condition, simple work-up, high yield as well as wide substrate scope, which makes this method powerful for one-pot synthesis of multi-substituted quinolines.
- Yu, Zhi-Hua,Zheng, Hu-Fei,Yuan, Wei,Tang, Zi-Long,Zhang, Ai-Dong,Shi, De-Qing
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p. 8137 - 8141
(2013/09/02)
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- Enantioselective copper-catalyzed reductive coupling of alkenylazaarenes with ketones
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Catalytic enantioselective methods for the preparation of chiral azaarene-containing compounds are of high value. By combining the utility of copper hydride catalysis with the ability of C=N-containing azaarenes to activate adjacent alkenes toward nucleophilic additions, the enantioselective reductive coupling of alkenylazaarenes with ketones has been developed. The process is tolerant of a wide variety of azaarenes and ketones, and provides aromatic heterocycles bearing tertiary-alcohol-containing side chains with high levels of diastereo- and enantioselection.
- Saxena, Aakarsh,Choi, Bonnie,Lam, Hon Wai
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p. 8428 - 8431
(2012/08/08)
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- Rare-earth-catalyzed C-H bond addition of pyridines to olefins
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An efficient and general protocol for the ortho-alkylation of pyridines via C-H addition to olefins has been developed, using cationic half-sandwich rare-earth catalysts, which provides an atom-economical method for the synthesis of alkylated pyridine der
- Guan, Bing-Tao,Hou, Zhaomin
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supporting information; experimental part
p. 18086 - 18089
(2012/01/03)
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- Palladium-catalyzed benzylic addition of 2-methyl azaarenes to N-sulfonyl aldimines via C-H bond activation
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Chemical equation presented An efficient protocol for the generation of amines by palladium-catalyzed nucleophilic benzylic addition of 2-methyl-substituted azaarenes to N-sulfonyl aldimines under neutral conditions via C-H bond activation has been developed. This reaction represents a very efficient methodology for the synthesis of heterocycle-containing amines and thus opens a new way to access amines through C-H bond activation.
- Qian, Bo,Guo, Shengmei,Shao, Jianping,Zhu, Qiming,Yang, Lei,Xia, Chungu,Huang, Hanmin
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supporting information; experimental part
p. 3650 - 3651
(2010/05/15)
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- Asymmetric transfer hydrogenation of quinolines using tethered Ru(II) catalysts
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The first report of an asymmetric transfer hydrogenation, in formic acid/triethylamine, of quinolines is described. Using a Ru(II) catalyst containing a 4-carbon tether, products of up to 73% ee were formed, whilst a Rh(III)-tethered catalyst gave products of up to 94% ee.
- Parekh, Vimal,Ramsden, James A.,Wills, Martin
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experimental part
p. 1549 - 1556
(2010/11/02)
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- Palladium-catalyzed coupling of N-heteroaryl sulfides with organozinc reagents
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The palladium-catalyzed cross-coupling of N-heteroaryl sulfides with organozinc reagents was developed. Scope and limitation of the reaction regarding generality of zinc reagents and substrate were also investigated.
- Koshiba, Takahiro,Miyazaki, Tohru,Tokuyama, Hidetoshi,Fukuyama, Tohru
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experimental part
p. 233 - 239
(2009/09/06)
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- Pyridine analogs as C5a antagonists
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The present invention provides novel compounds of Formula I which are antagonists of the C5a receptor. Compounds of the present invention are useful for the treatment of various C5a-mediated diseases and disorders; accordingly the present invention provid
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Page/Page column 21
(2008/06/13)
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- Concerning the mechanism of the Friedlaender quinoline synthesis
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Detailed experiments regarding the mechanism of the Friedlaender synthesis of quinolines from o-amino-benzaldehydes and simple aldehydes or ketones are described. Under the basic or acidic conditions commonly used in this reaction, it is concluded that the first step involves a slow intermolecular aldol condensation of the aldehyde or ketone with the o-aminobenzaldehyde. The aldol adduct 5 generated in this manner then undergoes very rapid cyclization to 4, which subsequently loses water to produce the quinoline derivative 8. Both 5 and 4 are too short lived to be detectable (TLC), even when deliberately generated by other means. It is also shown that E-enones corresponding to 6, i.e., the aldol dehydration product, are converted into quinolines (e.g., 21a and 21b from 17a and 17b) under basic or acidic conditions. Such enones are not detected as intermediates in the base-induced Friedlaender synthesis, even though certain congeners (17b) would be easily observable. Under acidic conditions these enones are too short lived to be detectable. Schiff bases derived from 2-aminobenzaldehyde (18a) and aldehydes or ketones can be generated under special conditions, but they show reactivity patterns different from those seen in the usual Friedlaender condensations. Thus, the ytterbium-triflate-catalyzed reaction of aldehydes with 18a at room temperature in toluene generates the E-Schiff bases (33, R1 = H), from which isomeric mixtures of tetrahydroquinoline derivatives 26 are formed exclusively. At higher temperatures, the E-Schiff bases 33 are isomerized to the Z-Schiff bases 34, from which the 3-substituted quinoline derivatives 24 are formed as the major products under appropriate conditions. Also, the ytterbium-triflate-catalyzed reaction of 18a with the pyrrolidine enamines of the methyl-n-alkylketones 38a,b produces mixtures in which the 2-monosubstituted kinetic products 37b,d predominate over the 2,3-disubstituted thermodynamic products 21c,e by a factor of 4:1 to 5:1. These results are opposite to those observed under the usual basic or acidic Friedlaender reactions with methyl-n-alkylketones, where the thermodynamic products are usually strongly favored. The unusual kinetic:thermodynamic product ratios observed with 38a,b are ascribed to the generation and rapid cyclization of mixtures of the Schiff bases 35 and 36, in which the kinetic isomer 35 is highly predominant.
- Muchowski, Joseph M.,Maddox, Michael L.
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p. 461 - 478
(2007/10/03)
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- Expeditious preparation of 2-substituted quinolines
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A library of 2-substituted quinolines was synthesized in solution from mixtures of Grignard reagents and a quinolinium salt. Grignard reagents were prepared in one pot, taking advantage of the entrainment method for their preparation from unreactive alkyl halides. Then mixtures of 2-alkylquinolines were readily accessible for biological tests or separated by centrifugal-partition chromatography (CPC) prior to the biological screening.
- Fakhfakh, Mohamed A.,Franck, Xavier,Fournet, Alain,Hocquemiller, Reynald,Figadère, Bruno
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p. 3847 - 3850
(2007/10/03)
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- ν-triazolines. Part 40. Thermal and photochemical transformations of 1-biaryl-5-amino-4,5-dihydro-ν-triazoles: A new synthetic approach to 6-alkylphenanthridines and aza-analogs
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1-Biaryl-5-morpholino-ν-triazolines 4 were prepared from aliphatic aldehydes 1, morpholine and 2-azidobiaryls 3. They underwent smooth thermal rearrangement to tertiary amidines 5 which were photochemically cyclized to 6-alkylphenanthridines 6a,b,e,f and analogs 6c,d and 8a,b with morpholine elimination. Direct photolysis of triazolines 4 afforded lower yields of the same compounds 6 together with by-products indicative of the mechanism of the photochemical rearrangement which is discussed.
- Erba, Emanuela,Pocar, Donato,Trimarco, Pasqualina
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p. 3535 - 3539
(2007/10/03)
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- Diels-Alder reaction of 1,2,3-benzotriazine with enamine: Application to the synthesis of alkaloids, 2-propylquinoline and 2-pentylquinoline
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The Diels-Alder reaction of 1,2,3-benzotriazine with several pyrrolidine enamines of carbonyl compounds was carried out in chloroform in the presence of zinc bromide to afford 2- or 3-mono-, or 2,3-disubstituted quinolines. This method was applied to the synthesis of the alkaloids, 2-propylquinoline and 2-pentylquinoline.
- Koyama, Junko,Toyokuni, Izumi,Tagahara, Kiyoshi
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p. 332 - 334
(2007/10/03)
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- Aggregative activation in heterocyclic chemistry. Part 5. Lithiation of pyridine and quinoline with the complex base BuLi·Me2N(CH2)2OLi (BuLi·LiDMAE)
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It is shown that the complex base BuLi·LiDMAE reacts with pyridine to give metallated species which, after trapping by electrophiles, lead to 2-substituted pyridines in good to excellent yields. The same reactions have been less successfully performed with quinoline.
- Gros, Philippe,Fort, Yves,Caubere, Paul
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p. 3597 - 3600
(2007/10/03)
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- Alkylation of Heteroaryl Halides by 2:1 Grignard Reagent/Cu(I) Mixtures.Synthesis of Alkylated Octahydrodibenzophenanhtrolines
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Treatment of 2-bromopyridine,3-bromopyridine,2-chloroquinoline,and 5,8-dichloro-1,2,3,4,9,10,11,12-octahydrodibenzophenanthroline(2) with a fourfold excess of 2:1 Grignard reagent/Cu(I) salt mixtures gives alkylated products in 50-85percent yield.Thus prepared are 2-methylpyridine,2-tert-butylpyridine,3-tert-butylpyridine,2-methylquinoline,2-ethylquinoline,2-tert-butylquinoline, and the dimethyl- and di-tert-butylphenanthrolines(3a) and (3b).Full experimental details are provided for the two phenanthrolines, which are prepared in four steps from o-phenylenediamine and ethyl 1-oxocyclohexane-2-carboxylate in 25-30percent overall yield.
- Bell, Thomas W.,Hu, Lain-Yen,Patel, Sanjay V.
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p. 3847 - 3850
(2007/10/02)
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- VISIBLE LIGHT- AND GAMMA RAY-INDUCED ALKYLATION IN PYRIDINE RING. EFFECTIVE ALKYLATION WITH VISIBLE LIGHT IN THE PRESENCE OF IRON(III) SULFATE
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Quinoline and 4-methylquinoline are alkylated with alkanecarboxylic acid upon visible light- or gamma-irradiation.In the photoalkylation, iron(III) sulfate not only accelerates the reaction, but also improves the selectivity for alkylation.Titanium oxide shows smaller effects than iron(III) sulfate.
- Sugimori, Akira,Yamada, Tetsuo
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p. 409 - 412
(2007/10/02)
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- Visible Light- and Radiation-Induced Alkylation of Pyridine Ring with Alkanoic Acid. Effective Alkylation in the Presence of Iron(III) Sulfate
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Quinoline and 4-methylquinoline are efficiently alkylated with alkanoic acid in the presence of iron(III) sulfate upon visible light-irradiation.Iron(III) sulfate not only accelerates the photoreaction but also increases the yield of alkylation.Gamma-irradiation also brings about the alkylation.In the photo- and radiation-induced alkylation with alkanoic acid, alkyl radicals play important roles.
- Sugimori, Akira,Yamada, Tetsuo
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p. 3911 - 3916
(2007/10/02)
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- Pharmaceutical compositions and methods of inhibiting gastric acid secretion
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Pharmaceutical compositions and methods of inhibiting gastric acid secretion by administering N-alkenyl and N-alkynyl thioamides.
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