- RhIII-Catalyzed Direct Heteroarylation of C(sp3)-H and C(sp2)-H Bonds in Heterocycles with N-Heteroaromatic Boronates
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Herein, we disclose a RhIII-catalyzed heteroarylation of C(sp3)-H and C(sp2)-H bonds in heterocycles with organoboron reagents. This protocol displays high efficiency and excellent functional group tolerance. A range of heterocyclic boronates with strong coordinating atoms, including pyridine, pyrimidine, pyrazole, thiophene, and furan derivatives, can be extensively served as the coupling reagents. The direct heteroarylation method could supply potential application in terms of the synthesis of drug molecules with multiple heterocycles.
- Wang, Huai-Wei,Wu, Jia-Xue,Qiao, Yu-Han,Li, Yong-Fei,Li, Da-Cheng,Dou, Jian-Min,Yao, Qing-Xia,Lu, Yi
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supporting information
p. 7177 - 7182
(2021/09/18)
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- Rhodium(III)-Catalyzed Direct Coupling of Quinoline-8-Carbaldehydes with (Het)Arylboronic Acids for the Synthesis of 8-Aryloylquinolines
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Herein, we describe a method for the synthesis of aryl-(het)aryl ketones by Rh(III)-catalyzed direct coupling between quinoline-8-carbaldehydes and (het)arylboronic acids. The method has a broad substrate scope, a high functional group tolerance, and uses
- Lyu, Xue-Li,Huang, Shi-Sheng,Huang, Yuan-Qiong,Li, Yong-Qiang,Song, Hong-Jian,Liu, Yu-Xiu,Wang, Qing-Min
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p. 10271 - 10282
(2020/09/03)
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- Cobalt-catalyzed ring-opening addition of azabenzonorbornadienes: Via C(sp3)-H bond activation of 8-methylquinoline
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The first ring-opening addition of a benzylic C(sp3)-H bond to azabenzonorbornadienes is demonstrated. The reaction proceeded under the catalytic system of [Cp?CoI2(CO)], AgSbF6 and Fe(OAc)2 in PhOMe. The methodology showed a good substrate scope with up to 96 yield. The relative configuration of the product was determined as cis-configuration by X-ray crystallography.
- Tan, Heng,Khan, Ruhima,Xu, Dandan,Zhou, Yongyun,Zhang, Xuexin,Shi, Guangrui,Fan, Baomin
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supporting information
p. 12570 - 12573
(2020/11/02)
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- Rh(iii)-Catalyzed straightforward arylation of 8-methyl/formylquinolines using diazo compounds
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A straightforward Rh(iii)-catalyzed general strategy was developed for the introduction of naphthol/phenol moieties to the C(sp3)-H bond of 8-methylquinoline using diazonaphthalen-2(1H)-ones/quinone diazides. The developed method was further extended towards the arylation of 8-formylquinolines to accomplish diarylketone derivatives. The method is simple, relatively rapid, and chemo and regioselective with a wide scope and functional group tolerance. The synthetic utility was established through gram-scale synthesis and biologically active molecule construction.
- Ghosh, Bidhan,Samanta, Rajarshi
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supporting information
p. 6886 - 6889
(2019/06/18)
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- Palladium-Catalyzed C-H Bond Functionalization Reactions Using Phosphate/Sulfonate Hypervalent Iodine Reagents
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A new and operationally simple approach for palladium-catalyzed C-H functionalization reactions utilizing an organophosphorus/sulfonate hypervalent iodine reagent as both an oxidant and the source of a functional group has been developed. Through this method, the oxidative phosphorylation-, sulfonation-, and hydroxylation of unactivated benzyl C(sp3)-H bonds, along with the hydroxylation and arylation of aryl C(sp2)-H bonds, are successfully realized under mild conditions and with excellent site-selectivity. The versatile C-OSO2R bond provides a platform for a wide array of subsequent diversification reactions.
- He, Yimiao,Huang, Lilan,Xie, Limei,Liu, Peng,Wei, Qiongmei,Mao, Fangfang,Zhang, Xuehong,Huang, Jun,Chen, Sijing,Huang, Chusheng
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p. 10088 - 10101
(2019/08/22)
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- A general method for the metal-free, regioselective, remote C-H halogenation of 8-substituted quinolines
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An operationally simple and metal-free protocol for geometrically inaccessible C5-H halogenation of a range of 8-substituted quinoline derivatives has been established. The reaction proceeds under air, with inexpensive and atom economical trihaloisocyanuric acid as a halogen source (only 0.36 equiv.), at room temperature. Exceptionally high generality with respect to quinoline is observed, and in most instances, the reaction proceeded with complete regioselectivity. Quinoline with a variety of substituents at the 8-position gave, exclusively, the C5-halogenated product in good to excellent yields. Phosphoramidates, tertiary amides, N-alkyl/N,N-dialkyl, and urea derivatives of quinolin-8-amine as well as alkoxy quinolines were halogenated at the C5-position via remote functionalization for the first time. This methodology provides a highly economical route to halogenated quinolines with excellent functional group tolerance, thus providing a good complement to existing remote functionalization methods of quinolin-8-amide derivatives and broadening the field of remote functionalization. The utility of the method is further showcased through the synthesis of several compounds of biological and pharmaceutical interest.
- Motati, Damoder Reddy,Uredi, Dilipkumar,Watkins, E. Blake
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p. 1782 - 1788
(2018/02/23)
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- Cp?Rh(III)-Catalyzed Mild Addition of C(sp3)-H Bonds to α,β-Unsaturated Aldehydes and Ketones
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A Rh(III)-catalyzed addition of benzylic C(sp3)-H bond to α,β-unsaturated ketones/aldehydes has been realized, leading to efficient synthesis of γ-aryl ketones/aldehydes. This atom-economic reaction proceeded under mild and redox-neutral conditions with a broad substrate scope. Besides benzylic C-H, allylic C-H bonds are also applicable when assisted by O-methyl ketoxime directing groups.
- Liu, Bingxian,Hu, Panjie,Zhou, Xukai,Bai, Dachang,Chang, Junbiao,Li, Xingwei
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supporting information
p. 2086 - 2089
(2017/04/28)
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- Cobalt(III)-Catalyzed Alkylation of Primary C(sp3)–H Bonds with Diazo Compounds
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Chelation-assisted C(sp2)–H metalation/carbenoid insertion has been well investigated. However, the analogous carbene functionalization of C(sp3)–H bonds remains a great challenge. Here we report the first cobalt(III)-catalyzed alkyl
- Yan, Sheng-Yi,Ling, Peng-Xiang,Shi, Bing-Feng
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supporting information
p. 2912 - 2917
(2017/09/08)
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- From Anilines to Quinolines: Iodide- and Silver-Mediated Aerobic Double C?H Oxidative Annulation–Aromatization
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Quinoline synthesis from easily accessible raw materials such as anilines is a valuable and meaningful task. Herein, we communicate an iodide- and silver-mediated C?H/C?H oxidative annulation–aromatization between anilines and allyl alcohols. This protocol provides a direct route to the synthesis of quinoline derivatives from inexpensive commodities. Various kinds of anilines, even heterocyclic anilines, were shown to be workable substrates, generating the corresponding multi-substituted quinolines in good yields.
- Wu, Jiwei,Liao, Zhixiong,Liu, Dong,Chiang, Chien-Wei,Li, Zheng,Zhou, Zhonghao,Yi, Hong,Zhang, Xu,Deng, Zixin,Lei, Aiwen
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supporting information
p. 15874 - 15878
(2017/10/23)
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- Rh-Catalyzed Direct Amination of Unactivated C(sp3)?H bond with Anthranils Under Mild Conditions
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C?N Bond formation is of great significance due to the ubiquity of nitrogen-containing compounds. Here, a mild and efficient RhIII-catalyzed C(sp3)?H aryl amination reaction is reported. Anthranil is employed as the nitrogen source with 100 % atom efficiency. This C?H amination reaction exhibits broad substrate scope without using any external oxidants. Mechanistic studies including rhodacycle intermediates, H–D exchange, kinetic isotope effect (KIE) experiments, and in situ IR are presented.
- Tang, Conghui,Zou, Miancheng,Liu, Jianzhong,Wen, Xiaojin,Sun, Xiang,Zhang, Yiqun,Jiao, Ning
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supporting information
p. 11165 - 11169
(2016/08/03)
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- Rhodium(III)-catalyzed intermolecular amidation with azides via C(sp 3)-H functionalization
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The amidation reactions of 8-methylquinolines with azides catalyzed by a cationic rhodium(III) complex proceed efficiently to give quinolin-8- ylmethanamine derivatives in good yields via C(sp3)-H bond activation under external oxidant-free conditions. A catalytically competent five-membered rhodacycle has been isolated and characterized, revealing a key intermediate in the catalytic cycle.
- Wang, Nuancheng,Li, Renhe,Li, Liubo,Xu, Shansheng,Song, Haibin,Wang, Baiquan
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p. 5379 - 5385
(2014/06/23)
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- Reduction of nitroarenes followed by propanol group transfer from tris(3-hydroxypropyl)- amine and cyclization leading to quinolines under heterogeneous Pd-C catalysis
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Nitroarenes having electron-donating or -withdrawing substituents are reduced to anilines and cyclized with tris(3- hydroxypropyl)amine in the presence of a catalytic amount of Pd-C along with tin(II) chloride and isopropanol in dioxane-H2O medium to give the corresponding quinolines in good to excellent yields. Copyright
- Cho, Chan Sik,Kim, Tae Gyun,Yoon, Nam Sik
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experimental part
p. 291 - 293
(2010/08/04)
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- Catalytic aerobic oxidation of substituted 8-methylquinolines in Pd II-2,6-pyridinedicarboxylic acid systems
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The ability of PdII complexes derived from 2,6- pyridinedicarboxylic acids to catalyze homogeneous regioselective aerobic oxidation of 5- and 6-substituted 8-methylquinolines in AcOH-Ac2O solution to produce corresponding 8-quinolylm
- Zhang, Jing,Khaskin, Eugene,Anderson, Nicholas P.,Zavalij, Peter Y.,Vedernikov, Andrei N.
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supporting information; body text
p. 3625 - 3627
(2009/02/06)
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- Aromatic Chlorination and Iodination of 8-Methylquinoline. Benzyl Bromination of 5-Halo-8-methylquinolines
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5-Chloro- and 5-iodo-8-methylquinoline were obtained by chlorination or iodination of 8-methylquinoline with chlorine or iodine in concentrated sulfuric acid in the presence of silver sulfate. 5-Fluoro-8-methylquinoline was synthesized from 5-amino-8-meth
- Tochilkin, A. I.,Gracheva, I. N.,Kovel'man, I. R.,Prokof'ev, E. P.
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p. 1093 - 1096
(2007/10/02)
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