- 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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- Synthesis and biological evaluation of 2-phenyl-4-aminoquinolines as potential antifungal agents
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Abstract: A series of 2-phenyl-4-aminoquinolines were designed, synthesized and evaluated for their antifungal activities against three phytopathogenic fungi in vitro. All of the target compounds were fully elucidated by 1H NMR, 13C
- Yang, Rui,Du, Wenhao,Yuan, Huan,Qin, Tianhong,He, Renxiao,Ma, Yanni,Du, Haiying
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p. 1065 - 1075
(2020/11/09)
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- Synthesis, in vitro and in vivo biological evaluation of novel graveolinine derivatives as potential anti-Alzheimer agents
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A novel series of graveolinine derivatives were synthesized and evaluated as potential anti-Alzheimer agents. Compound 5f exhibited the best inhibitory activity for acetylcholinesterase (AChE) and had surprisingly potent inhibitory activity for butyrylcho
- Luo, Wen,Lv, Jian-Wu,Wang, Ting,Zhang, Zhi-Yang,Guo, Hui-Yan,Song, Zhi-Yi,Wang, Chao-Jie,Ma, Jing,Chen, Yi-ping
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- Direct arylation for the synthesis of 2-arylquinolines from N-methoxyquinoline-1-ium tetrafluoroborate salts and arylboronic acids
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A rapid and direct arylation reaction of N-methoxyquinoline-1-ium tetrafluoroborate derivatives and arylboronic acids with high regioselectivety at room temperature was discovered. The reaction shows exceptional functional group tolerance and broad substrate scope regarding both the quinoline derivatives and the arylboronic acids.
- Ren, Xiaoxiao,Han, Shuaijun,Gao, Xianying,Li, Jingya,Zou, Dapeng,Wu, Yangjie,Wu, Yusheng
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p. 1065 - 1068
(2018/02/19)
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- Photoredox-mediated Minisci C-H alkylation of N-heteroarenes using boronic acids and hypervalent iodine
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A photoredox-mediated Minisci C-H alkylation reaction of N-heteroarenes with alkyl boronic acids is reported. A broad range of primary and secondary alkyl groups can be efficiently incorporated into various N-heteroarenes using [Ru(bpy)3]Cl2 as photocatalyst and acetoxybenziodoxole as oxidant under mild conditions. The reaction exhibits excellent substrate scope and functional group tolerance, and offers a broadly applicable method for late-stage functionalization of complex substrates. Mechanistic experiments and computational studies suggest that an intramolecularly stabilized ortho-iodobenzoyloxy radical intermediate might play a key role in this reaction system.
- Li, Guo-Xing,Morales-Rivera, Christian A.,Wang, Yaxin,Gao, Fang,He, Gang,Liu, Peng,Chen, Gong
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p. 6407 - 6412
(2016/09/28)
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- Chemoselective chromium(II)-catalyzed cross-coupling reactions of dichlorinated heteroaromatics with functionalized aryl Grignard reagents
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Chromium(II) chloride catalyzes the chemoselective cross-coupling reaction of dichloropyridines with a range of functionalized (hetero)aromatic Grignard reagents at room temperature. Functional groups, such as esters and acetals, are well tolerated in this transformation. Previously challenging substrates, quinolines and isoquinolines, participate in the selective Cr-catalyzed cross-coupling in cyclopentyl methyl ether (CPME) as the solvent. The effective purging of Cr salts is demonstrated by using various solid supports.
- Steib, Andreas K.,Kuzmina, Olesya M.,Fernandez, Sarah,Malhotra, Sushant,Knochel, Paul
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supporting information
p. 1961 - 1965
(2015/01/30)
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- Rewiring chemistry: Algorithmic discovery and experimental validation of one-pot reactions in the network of organic chemistry
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Computational algorithms are used to identify sequences of reactions that can be performed in one pot. These predictions are based on over 86 000 chemical criteria by which the putative sequences are evaluated. The "raw" algorithmic output is then validated experimentally by performing multiple two-, three-, and even four-step sequences. These sequences "rewire" synthetic pathways around popular and/or important small molecules. Copyright
- Gothard, Chris M.,Soh, Siowling,Gothard, Nosheen A.,Kowalczyk, Bartlomiej,Wei, Yanhu,Baytekin, Bilge,Grzybowski, Bartosz A.
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supporting information; experimental part
p. 7922 - 7927
(2012/09/08)
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- Synthesis of 2,4-diarylquinolines: Nickel-catalysed ligand-free cross-couplings of 4-chloro-2-arylquinolines with arylmagnesium halides in 2-methyltetrahydrofuran
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A ligand-free and room temperature protocol for the synthesis of 2,4-diarylquinolines is described. Treatment of 4-chloro-2-arylquinolines with arylmagnesium halides in the presence of a catalytic amount of nickel(II) chloride without ligands in 2-methylt
- Li, Zhenhua,Xu, Lingmin,Su, Weike
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scheme or table
p. 240 - 242
(2011/07/29)
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- Potent DNA-directed alkylating agents: Synthesis and biological activity of phenyl N-mustard-quinoline conjugates having a urea or hydrazinecarboxamide linker
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A series of N-mustard-quinoline conjugates bearing a urea or hydrazinecarboxamide linker was synthesized for antitumor evaluation. The in vitro cytotoxicity studies revealed that compounds with hydrazinecarboxamide linkers were generally more cytotoxic th
- Kakadiya, Rajesh,Dong, Huajin,Kumar, Amit,Narsinh, Dodia,Zhang, Xiuguo,Chou, Ting-Chao,Lee, Te-Chang,Shah, Anamik,Su, Tsann-Long
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supporting information; experimental part
p. 2285 - 2299
(2010/06/14)
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- NUCLEIC ACID FLUORESCENT STAINS
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The present invention provides fluorescent dye compounds and methods of using the compounds for the staining of nucleic acids. In particular, the dye compounds comprise heterocyclic molecules with hydroxy alkyl and aromatic substituents, and the dye compo
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Page/Page column 24
(2009/06/27)
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- A novel one-pot oxidative deformylation of N-formyldihydroquinolines employing ferric chloride hexahydrate. Synthesis of 4-chloro-2-phenylquinolines and 4-chloro-2-(1,3-diphenyl-1H-pyrazol-4-yl)quinolines
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(Chemical Equation Presented) A novel versatile one-pot oxidative deformylation approach has been developed to synthesize 4-chloro-2- phenylquinolines and 4-chloro-2-(1,3-diphenyl-1H-pyrazol-4-yl)quinolines from the corresponding N-formyldihydroquinolines
- Kumar, Kalvi Hemanth,Perumal, Paramasivan T.
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p. 597 - 599
(2008/09/19)
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- Investigation of amination in 4-chloro-2-phenylquinoline derivatives with amide solvents
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Novel 4-amino-2-phenylquinoline derivatives were synthesized by reacting various 4-chloro-2-arylquinoline compounds having activated chloro group with the corresponding amide solvents at reflux for overnight. The activity of amination by the amide solvent
- Tsai, Jui-Ying,Chang, Chih-Shiang,Huang, Yi-Fan,Chen, Hua-Shin,Lin, Shao-Kai,Wong, Fung Fuh,Huang, Li-Jiau,Kuo, Sheng-Chu
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supporting information; experimental part
p. 11751 - 11755
(2009/04/05)
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- HETEROCYCLIC AND BICYCLIC COMPOUNDS, COMPOSITIONS AND METHODS
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The present invention provides, among other things, new bicyclo heterocyclic compounds, compositions comprising these heterocyclic compounds, methods of making the heterocyclic compounds, and methods of using these heterocyclic compounds for treating a variety of conditions and disease states associated with, for example, cellular proliferation, inflammation, glycosidase expression, or the low expression of Perlecan.
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Page/Page column 122
(2010/11/08)
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- PYRIDIN-4-YLAMINE COMPOUNDS USEFUL IN THE TREATMENT OF NEUROPATHIC PAIN
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The present invention is directed to a method of use of triazolo-pyridazine compounds in the treatment of neuropathic pain. The present invention is also directed to the use of triazolo-pyridazine compounds in the treatment of psychiatric and mood disorde
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Page/Page column 45
(2010/02/11)
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- Use of highly active palladium-phosphinous acid catalysts in Stille, Heck, amination, and thiation reactions of chloroquinolines
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An efficient synthetic route toward a variety of 2,4-disubstituted quinolines has been developed. Alkylation and arylation of 4-chloroquinoline using organolithium reagents proceed with high regioselectivity in position 2 under cryogenic conditions. The intermediate 1,2-dihydro-4-chloro-quinoline derivatives are unstable to air and are easily oxidized to the corresponding 2-substituted 4-chloroquinolines in high yields. Highly active palladium-phosphinous acid catalysts POPd, POPd1, and POPd2 have been employed in Stille cross-couplings of quinaldine with arylstannanes and in Heck additions of various 2-substituted 4-chloroquinolines to tert-butyl acrylate. In particular, POPd combines high catalytic activity for cross-coupling reactions with simplicity of use due to its stability to air. Utilizing CsF in POPd-catalyzed Stille couplings further increased the reactivity of arylstannanes, which was attributed to the fluorophilicity of organotin compounds. Basic additives were found to exhibit a significant effect on the yields of the POPd-promoted Heck reactions. In general, dicyclohexylmethylamine affords superior results than NaOAc, Cs2CO3, or t-BuOK. POPd was also found to tolerate amine and thiol substrates and proved to promote carbon-heteroatom bond formation of chloroquinoline derivatives with aliphatic and aromatic amines and thiols, respectively.
- Wolf, Christian,Lerebours, Rachel
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p. 7077 - 7084
(2007/10/03)
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- Regioselective reactions of organozinc reagents with 2,4- dichloroquinoline and 5,7-dichloropyrazolo[1,5-α]pyrimidine
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Strategies for controlling the regioselective reactions between 2,4- dichloroquinoline and organozinc reagents are described. 2,4- Dichloroquinoline has been found to react with benzylic zinc and phenylzinc reagents in the presence of catalytic amounts of palladium complexes to exclusively give α-substituted products. Several metal salts were examined as an additive for γ-selective coupling reactions. The most effective additive for selective coupling reaction at the γ-position has been found to be LiCl. These conditions for α- or γ-selective coupling reactions were applied to the reaction between 5,7-dichloropyrazolo[1,5-α]pyrimidine and a biphenylmethylzinc reagent in the synthesis of the angiotensin II receptor antagonists. This regioselectivity should be generally applicable to other α,γ-dichloroazine systems.
- Shiota, Takeshi,Yamamori, Teruo
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p. 453 - 457
(2007/10/03)
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- Synthesis and structure-activity relationships of 9-substituted acridines as endothelin-A receptor antagonists
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Screening of a compound library against endothelin receptors (ET(A) and ET(B)) revealed PD 102566 (compound 1) as an ET(A) selective antagonist. Synthesis and structure-activity relationships (SAR) of a series of analogs are described.
- Cheng,Lee,Klutchko,Winters,Reynolds,Welch,Flynn,Doherty
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p. 2999 - 3002
(2007/10/03)
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- Quinoline Nitroxide Radicals. Ipso-Attack in the Reaction between 2-Methoxy and 2-Cyanoquinoline N-oxide, and Phenylmagnesium Bromide
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2-Methoxy and 2-cyanoquinoline N-oxide, when treated with phenylmagnesium bromide, undergo a nucleophilic ipso-attack at C-2, yielding, by elimination of methoxymagnesium bromide or cyanomagnesium bromide, the corresponding 2-phenylquinoline N-oxides, which react with the excess of Grignard reagents forming 2,2-diphenylquinoline 1-oxyls.Even when the methoxy and cyano groups are in position 4, the attack by the Grignard reagent takes place at C-2 giving 2-phenylquinolines and 2-phenylquinoline N-oxides by elimination by hydroxymagnesium bromide and bromomagnesium hydride, respectively; the formation of 2,2-diphenylquinoline 1-oxyls in these reactions is discussed.
- Colonna, Martino,Greci, Lucedio,Poloni, Marino
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p. 293 - 297
(2007/10/02)
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