- Xantphos-Capped Pd(II) and Pt(II) Macrocycles of Aryldithiolates: Structural Variation and Catalysis in C-C Coupling Reaction
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The self-assembly of Xantphos-capped M(OTf)2 (M = cis-[M′(Xantphos)]2+ M′ = Pd, Pt) with bridging ligands 1,4-benezenedithiol or 4,4′-biphenyldithiol has been investigated. The reactions have yielded complexes [M{S(C6H4)nSH}]2(OTf)2 (I) and [M2{S(C6H4)nS}]2(OTf)4 (II) (n = 1 or 2). The equilibrium between I and II has been established in platinum complexes for n = 2, whereas the analogous Pd complex exclusively exist as II. These results are different from our previously reported dppe or triethyl phosphine-capped complexes which showed only type II. The same reaction with 1,3-benezenedithiol lead to the complex [M2(SC6H4SSC6H4S)](OTf)2 (III), containing a S-S bond between two thiolate ligands, formed via a complex of type I in solution. Characterization of the complexes was accomplished by NMR spectroscopy, UV-vis spectroscopy and mass spectrometry, and X-ray crystallography. Density functional calculations were performed to estimate the relative stability of three types of complexes. The palladium complexes are excellent catalysts in Suzuki C-C cross coupling reactions under mild conditions, and can be reused eight times without losing significant yield. The activity of the Pd catalysts derived from three dithiol ligand follows opposite trend of the stability as III > II > I. The comparative catalytic activity of the tetranuclear Pd complexes (II) of bis-phosphines of varied bite angles, including the structurally characterized [Pd2(dppf)2(SC12H8S)]2(OTf)4 has also been demonstrated.
- Mane, Pravin A.,Dey, Sandip,Pathak, Arup Kumar,Kumar, Mukesh,Bhuvanesh, Nattamai
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Read Online
- Minisci-Type Alkylation of N-Heteroarenes by N-(Acyloxy)phthalimide Esters Mediated by a Hantzsch Ester and Blue LED Light
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A synthetic method that enables the Hantzsch ester-mediated Minisci-type C2-alkylation of quinolines, isoquinolines and pyridines by N-(acyloxy)phthalimide esters (NHPI) under blue LED (light emitting diode) light (456 nm) is described. Achieved under mild reaction conditions at room temperature, the metal-free synthetic protocol was shown to be applicable to primary, secondary and tertiary NHPIs to give the alkylated N-heterocyclic products in yields of 21–99%. On introducing a chiral phosphoric acid, an asymmetric version of the reaction was also realised and provided product enantiomeric excess (ee) values of 53–99%. The reaction mechanism was delineated to involve excitation of an electron-donor acceptor (EDA) complex, formed from weak electrostatic interactions between the Hantzsch ester and NHPI, which generates the posited radical species of the redox active ester that undergoes addition to the N-heterocycle.
- Kyne, Sara Helen,Li, Jiacheng,Siang Tan, Suan,Wai Hong Chan, Philip
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supporting information
(2022/01/11)
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- Iron(II)-Catalyzed Aerobic Biomimetic Oxidation of N-Heterocycles
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Herein, an iron(II)-catalyzed biomimetic oxidation of N-heterocycles under aerobic conditions is described. The dehydrogenation process, involving several electron-transfer steps, is inspired by oxidations occurring in the respiratory chain. An environmentally friendly and inexpensive iron catalyst together with a hydroquinone/cobalt Schiff base hybrid catalyst as electron-transfer mediator were used for the substrate-selective dehydrogenation reaction of various N-heterocycles. The method shows a broad substrate scope and delivers important heterocycles in good-to-excellent yields.
- Manna, Srimanta,Kong, Wei-Jun,B?ckvall, Jan-E.
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supporting information
p. 13725 - 13729
(2021/09/08)
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- Time-Resolved EPR Revealed the Formation, Structure, and Reactivity of N -Centered Radicals in an Electrochemical C(sp3)-H Arylation Reaction
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Electrochemical synthesis has been rapidly developed over the past few years, while a vast majority of the reactions proceed through a radical pathway. Understanding the properties of radical intermediates is crucial in the mechanistic study of electroche
- Alhumade, Hesham,Gao, Renfei,Huang, Cunlong,Lei, Aiwen,Liu, Yichang,Liu, Zhao,Qi, Xiaotian,Shi, Biyin,Wang, Shengchun
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supporting information
p. 20863 - 20872
(2021/12/14)
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- Method for preparing 2 -arylquinoline from 4 -amino diaryl methanol
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The invention discloses a method for preparing 2 - arylquinoline from 4 -amino diaryl methanol, wherein 2 -aminodiarylmethanol is heated and converted into DMSO arylquinoline compounds under the action of alkali under an oxygen-containing atmosphere in a mixed solution of formaldehyde and 4 . In 4 -arylquinoline compound structure prepared by the method 2-position carbon atoms are provided DMSO, 3-bit carbon atoms are provided by formaldehyde, and all other atoms in the quinoline compound structure are provided by the raw material o-amino aryl methanol. The method for synthesizing 4 - arylquinoline has the advantages of wide raw material sources, environmental friendliness, low price and simple operation, and is beneficial to industrial production.
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Paragraph 0041-0050
(2021/10/27)
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- Unexpected Annulation between 2-Aminobenzyl Alcohols and Benzaldehydes in the Presence of DMSO: Regioselective Synthesis of Substituted Quinolines
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An unexpected annulation among 2-aminobenzyl alcohols, benzaldehydes, and DMSO to quinolines has been disclosed. For the reported annulation between 2-aminobenzyl alcohols and benzaldehydes, the change of the solvent from toluene to DMSO led to the change of the product from the diheteroatomic cyclic benzoxazines to monoheteroatomic cyclic quinolines. This annulation can be used to synthesize regioselectively different substituted quinolines by the choice of different 2-amino alcohols, aldehydes, and sulfoxides as substrates. Interestingly, introducing substituent groups to the α-position of sulfoxides resulted in the interchange of the positions between benzaldehydes and sulfoxides in the product quinolines. On the basis of the control experiments and literatures, a plausible mechanism for this annulation was proposed.
- Yang, Tonglin,Nie, Zhi-Wen,Su, Miao-Dong,Li, Hui,Luo, Wei-Ping,Liu, Qiang,Guo, Can-Cheng
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p. 15228 - 15241
(2021/10/25)
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- PEG-400 as a carbon synthon: Highly selective synthesis of quinolines and methylquinolines under metal-free conditions
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A metal-free, peroxide-free, and efficient procedure for the highly selective synthesis of quinolines and methylquinolines was reported. The main feature of this method was that the same substrate can produce quinolines and methylquinolines, respectively, under different reaction conditions. PEG-400 was used as both a reactant and solvent in this reaction. The utility of the designed procedure was also demonstrated by the derivatization of the products to bioactive compounds. This journal is
- Ding, Chengcheng,Feng, Kaili,Li, Shichen,Ma, Chen
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supporting information
p. 5542 - 5548
(2021/08/16)
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- Synthesis of Quinolines via the Metal-free Visible-Light-Mediated Radical Azidation of Cyclopropenes
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We report the synthesis of quinolines using cyclopropenes and an azidobenziodazolone (ABZ) hypervalent iodine reagent as an azide radical source under visible-light irradiation. Multisubstituted quinoline products were obtained in 34-81% yield. The reaction was most efficient for 3-trifluoromethylcyclopropenes, affording valuable 4-trifluoromethylquinolines. The transformation probably proceeds through the cyclization of an iminyl radical formed by the addition of the azide radical on the cyclopropene double bond, followed by ring-opening and fragmentation.
- Smyrnov, Vladyslav,Muriel, Bastian,Waser, Jerome
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p. 5435 - 5439
(2021/07/21)
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- Synthesis of 4-substituted-1,2-dihydroquinolines by means of gold-catalyzed intramolecular hydroarylation reaction of n-ethoxycarbonyl-n-propargylanilines
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An alternative Au(I)-catalyzed synthetic route to functionalized 1,2-dihydroquinolines is reported. This novel approach is based on the use of N-ethoxycarbonyl protected-Npropargylanilines as building blocks that rapidly undergo the IMHA reaction affording the 6-endo cyclization product in good to high yields. In the presence of N-ethoxycarbonyl-N-propargyl-metasubstituted anilines, the regiodivergent cyclization at the ortho-/para-position is achieved by the means of catalyst fine tuning.
- Arcadi, Antonio,Calcaterra, Andrea,Fabrizi, Giancarlo,Fochetti, Andrea,Goggiamani, Antonella,Iazzetti, Antonia,Marrone, Federico,Marsicano, Vincenzo,Mazzoccanti, Giulia,Serraiocco, Andrea
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- Copper-mediated formal [5+1] annulation of 2-vinylanilines and glyoxylic acid: A facile approach for the synthesis of 4-arylated quinolines
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A copper-mediated formal [5 + 1] oxidative annulation of 2-vinylanilines and glyoxylic acid to 4-arylated quinolines was developed. A series of 4-arylated quinoline derivatives were obtained in good to excellent yields. This protocol could be carried out efficiently on gram scale. The transformation probably underwent nucleophilic addition/6π electrocyclization/oxidative aromatization and the elimination of CO2 cascade processes.
- Xiang, Yunyu,Luo, Puying,Hao, Tianxin,Xiong, Weikang,Song, Xiaolin,Ding, Qiuping
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- Superacid-promoted synthesis of quinoline derivatives
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A series of vinylogous imines have been prepared from anilines and cinnamaldehydes. These substrates react in superacidic media to provide quinolines and related compounds. A mechanism for the conversion is proposed which involves the cyclization of dicationic superelectrophilic intermediates. Aromatization of the quinoline ring is thought to occur by superacid-promoted elimination of benzene.
- Klumpp, Douglas A.,Stentzel, Michael R.,Vuong, Hein
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- Dearomative Photocatalytic Construction of Bridged 1,3-Diazepanes
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The construction of diverse sp3-rich skeletal ring systems is of importance to drug discovery programmes and natural product synthesis. Herein, we report the photocatalytic construction of 2,7-diazabicyclo[3.2.1]octanes (bridged 1,3-diazepanes) via a reductive diversion of the Minisci reaction. The fused tricyclic product is proposed to form via radical addition to the C4 position of 4-substituted quinoline substrates, with subsequent Hantzsch ester-promoted reduction to a dihydropyridine intermediate which undergoes in situ two-electron ring closure to form the bridged diazepane architecture. A wide scope of N-arylimine and quinoline derivatives was demonstrated and good efficiency was observed in the construction of sterically congested all-carbon quaternary centers. Computational and experimental mechanistic studies provided insights into the reaction mechanism and observed regioselectivity/diastereoselectivity.
- Dixon, Darren J.,Duarte, Fernanda,Leitch, Jamie A.,Rogova, Tatiana
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supporting information
p. 4121 - 4130
(2020/02/05)
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- DMSO/t-BuONa/O2-Mediated Aerobic Dehydrogenation of Saturated N-Heterocycles
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Aromatic N-heterocycles such as quinolines, isoquinolines, and indolines are synthesized via sodium tert-butoxide-promoted oxidative dehydrogenation of the saturated heterocycles in DMSO solution. This reaction proceeds under mild reaction conditions and has a good functional group tolerance. Mechanistic studies suggest a radical pathway involving hydrogen abstraction of dimsyl radicals from the N-H bond or α-C-H of the substrates and subsequent oxidation of the nitrogen or α-aminoalkyl radicals.
- Cai, Hu,Tan, Wei,Xie, Yongfa,Yang, Ruchun,Yue, Shusheng
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p. 7501 - 7509
(2020/07/07)
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- MnOx/catechol/H2O: A cooperative catalytic system for aerobic oxidative dehydrogenation of N-heterocycles at room temperature
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Amorphous manganese oxide doped by Na+ ion (Na-AMO) was successfully prepared and found to be an efficient heterogeneous catalyst in aerobic oxidative dehydrogenation of N-heterocycles, cooperate with catechol. Na-AMO was fully characterized by XRD, XPS BET H2-TPR, CO2-TPD FT-IR, TEM, SEM and had rich amounts of surface absorbed active oxygen species which are responsible for superior catalytic performance. The synergistic interaction between Na-AMO and catechol makes catalytic system efficient and tolerant, which offers various N-heterocycles in good to excellent yields under mild conditions.
- Tang, Tao,Bi, Xiuru,Meng, Xu,Chen, Gexin,Gou, Mingxia,Liu, Xiang,Zhao, Peiqing
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- Aerobic oxidative dehydrogenation of N-heterocycles over OMS-2-based nanocomposite catalysts: Preparation, characterization and kinetic study
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OMS-2-based nanocomposites doped with tungsten were prepared for the first time and their remarkably enhanced catalytic activity and recyclability in aerobic oxidative dehydrogenation of N-heterocycles were examined in detail. Many tetrahydroquinoline derivatives and a broad range of other N-heterocycles could be tolerated by the catalytic system using a biomass-derived solvent as a reaction medium. Newly generated mixed crystal phases, noticeably enhanced surface areas and labile lattice oxygen of the OMS-2-based nanocomposite catalysts might contribute to their excellent catalytic performance. Moreover, a kinetic study was extensively performed which concluded that the dehydrogenation of 1,2,3,4-tetrahydroquinoline is a first-order reaction, and the apparent activation energy is 29.66 kJ mol-1
- Bi, Xiuru,Tang, Tao,Meng, Xu,Gou, Mingxia,Liu, Xiang,Zhao, Peiqing
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p. 360 - 371
(2020/02/04)
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- A Highly Efficient Monophosphine Ligand for Parts per Million Levels Pd-Catalyzed Suzuki–Miyaura Coupling of (Hetero)Aryl Chlorides
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A new indolylphosphine WK-phos has been synthesized for Pd-catalyzed Suzuki–Miyaura coupling of (hetero)aryl chlorides with (alkyl)arylboronic acids. Comprising this newly developed ligand with palladium(II) acetate, the resulting catalyst system was found to be highly effective in facilitating the reaction even when the catalyst loading reaches parts per million levels (e.g. 10 ppm). These examples represent one of the lowest catalyst loadings reported to date of employing monophosphine (e.g. Ar-PCy2) for Suzuki–Miyaura reactions. The ligand geometry has also been well-characterized by single-crystal X-ray crystallography.
- Choy, Pui Ying,Yuen, On Ying,Leung, Man Pan,Chow, Wing Kin,Kwong, Fuk Yee
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p. 2846 - 2853
(2020/04/09)
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- Lewis acid catalyzed reactivity switch: Pseudo three-component annulation of nitrosoarenes and (epoxy)styrenes
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A Lewis acid catalyzed annulation reaction via arene functionalization of nitrosoarenes and C-C cleavage of (epoxy)styrene to provide arylquinolines is reported. The Lewis acid catalyst altered the annulation pattern providing arylquinolines instead of oxazolidines. The reaction with styrene resulted in a mixture of 2,4-diarylquinoline and 4-Arylquinoline, while only 3-Arylquinoline was formed from the reaction of epoxystyrene. This journal is
- Purkait, Anisha,Saha, Subhajit,Ghosh, Santanu,Jana, Chandan K.
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supporting information
p. 15032 - 15035
(2020/12/22)
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- NaH-mediated direct C-H arylation in the presence of 1,10-phenanthroline
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Transition-metal-free coupling of haloarenes with unactivated arenes has been developed in the presence of NaH and 1,10-phenanthroline. Various haloarenes bearing methyl, methoxy, halogen (fluoride, chloride, and bromide), cyano, trifluoromethyl, ester, and amide groups can be cross-coupled with unactivated arenes, or heteroarenes in this reaction.
- Nozawa-Kumada, Kanako,Iwakawa, Yuki,Onuma, So,Shigeno, Masanori,Kondo, Yoshinori
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supporting information
p. 7773 - 7776
(2020/07/27)
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- Quinoline compound and synthesis method thereof
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The invention discloses a synthesis method of a quinoline compound. The synthesis method comprises the following steps: adding a diazocarbonyl compound and a 2-vinylaniline compound into a solvent, carrying out a reaction under the protection of an inert
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Paragraph 0171-0175
(2020/02/14)
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- CONVERSION OF TETRAHYDROQUINOLINE DERIVATIVES TO QUINOLINE USING AZOCOMPOUND
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The present invention relates to a method of converting tetrahydroquinoline derivatives into quinoline using an azo compound and, more specifically, to a conversion method which is performed in a deuterium chloroform (CDCl_3) or chloroform (CHCl_3) solution including dialkyl azodicarboxylate, which is a method of producing quinoline through a dehydrogenation reaction of 1,2,3,4-tetrahydroquinoline. According to the present invention, a dehydrogenation reaction rate is dependent on the electronic and steric properties of used dialkyl azodicarboxylate; and chloroform shows better results than other substances in solvents screened with diethyl azodicarboxylate. Various types of 1,2,3,4-tetrahydroquinoline undergo the dehydration reaction of the present invention to produce the corresponding quinoline in a yield of at least 90%; and diethyl hydrazo dicarboxylate, which is a reduced form of diethyl azodicarboxylate, is readily separated and recyclable.COPYRIGHT KIPO 2020
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Paragraph 0041-0042; 0092; 0112-0116
(2020/03/10)
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- Method for synthesizing substituted quinoline derivative 4- through palladium catalysis (by machine translation)
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The invention belongs to the technical field of 4 - synthetic chemistry, and particularly. relates to a method for synthesizing a substituted quinoline derivative with palladium through palladium catalysis, Cs. 2 CO3 The method disclosed by, the 60-80 °C invention is 5-8 simple, and green, in 4 - synthetic process,has excellent selectivity and high yield, and has a wide substrate range, and the method has a wide, application value in the fields of pharmaceutical chemistry, biochemistry and the like. (by machine translation)
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Paragraph 0041-0043
(2020/01/08)
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- A Monophosphine Ligand Derived from Anthracene Photodimer: Synthetic Applications for Palladium-Catalyzed Coupling Reactions
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Herein, we present an air-stable dianthracenyl monophosphine ligand (diAnthPhos) which can be prepared in two steps from commercially available anthracene derivatives. The ligand exhibits excellent efficiency for palladium-catalyzed coupling reactions. In particular, Miyaura borylation of heterocycle-containing electrophiles can be facilitated employing the diAnthPhos ligand with a broad substrate scope and low catalyst loading. The valuable synthetic utility of the new ligand is further demonstrated by a one-pot Miyaura borylation/Suzuki coupling protocol for heteroaryl-containing substrates.
- Wang, Xin,Liu, Wei-Gang,Tung, Chen-Ho,Wu, Li-Zhu,Cong, Huan
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p. 8158 - 8163
(2019/09/07)
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- Cobalt(III)-Catalyzed, DMSO-Involved, and TFA-Controlled Regioselective C?H Functionalization of Anilines with Alkynes for Specific Assembly of 3-Arylquinolines
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Herein, a novel cobalt(III)-catalyzed and TFA-controlled [3+2+1] cyclization of diverse anilines and terminal alkynes has been realized by using DMSO as both the solvent and the C1 source, which led to the specific synthesis of privileged 3-arylquinolines in one pot and regioselectively. Mechanistic investigations revealed that this versatile transformation might be initiated with a C?H activation process and with a 2-vinylbenzenamine species as the active intermediate. (Figure presented.).
- Zhang, Peiquan,Yang, Yurong,Chen, Zhiyong,Xu, Zhang,Xu, Xuefeng,Zhou, Zhi,Yu, Xiyong,Yi, Wei
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p. 3002 - 3007
(2019/04/30)
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- Microwave-Assisted Metal-Free Rapid Synthesis of C4-Arylated Quinolines via Povarov Type Multicomponent Reaction
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A rapid microwave assisted, (±) camphor-10-sulfonic acid (CSA) promoted, Povarov type multicomponent synthesis of 4-arylated quinolines from anilines, alkynes, and paraformaldehyde is described. This reaction proceeds through [4+2] cycloaddition of imine (formed in situ from aniline and paraformaldehyde) and alkynes in the presence of CSA, without any metal catalyst. Mechanistic study revealed that CSA inhibit the synthesis of Troger's base and assist the cycloaddition of imines with alkynes by activating the imine.
- Chandra, Devesh,Dhiman, Ankit Kumar,Kumar, Rakesh,Sharma, Upendra
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p. 2753 - 2758
(2019/04/08)
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- Direct Synthesis of Quinolines via Co(III)-Catalyzed and DMSO-Involved C-H Activation/Cyclization of Anilines with Alkynes
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A unique Co(III)-catalyzed and DMSO-involved C-H activation/cyclization of simple, cheap, and easily available anilines with alkynes for direct and highly efficient synthesis of privileged quinolines with exclusive regioselectivity and broad substrate/functional group tolerance and in good to excellent yields, where DMSO was employed as both the solvent and the C1 building block of quinoline products, is reported. Mechanistic experiments revealed that the versatile reaction might employ the 2-vinylbenzenamine species as the active intermediate.
- Xu, Xuefeng,Yang, Yurong,Zhang, Xu,Yi, Wei
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supporting information
p. 566 - 569
(2018/02/10)
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- Efficient dehydrogenation of 1,2,3,4-tetrahydroquinolines mediated by dialkyl azodicarboxylates
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Various dialkyl azodicarboxylates were investigated for the dehydrogenation of 1,2,3,4-tetrahydroquinolines to quinolines. The dehydrogenation rates varied according to the electronic and steric nature of the used dialkyl azodicarboxylates. Among solvents screened with diethyl azodicarboxylate, chloroform exhibited superior results to others. A variety of 1,2,3,4-tetrahydroquinolines underwent the present dehydrogenation to produce the corresponding quinolines. Diethyl hydrazodicarboxylate, which is a reduced species of diethyl azodicarboxylate, was easily separated for recycle.
- Bang, Saet Byeol,Kim, Jinho
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p. 1291 - 1298
(2018/04/05)
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- Oxidation Potential Tunable Organic Molecules and Their Catalytic Application to Aerobic Dehydrogenation of Tetrahydroquinolines
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In this work, oxidation potential tunable organic molecules, alkyl 2-phenyl hydrazocarboxylates, were disclosed. The exquisite tuning of their oxidation potentials facilitated a catalytic dehydrogenation of 1,2,3,4-tetrahydroquinolines in the presence of Mn(Pc) and O2.
- Jung, Dahyeon,Jang, Seol Heui,Yim, Taeeun,Kim, Jinho
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supporting information
p. 6436 - 6439
(2018/10/15)
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- Direct Assembly of 4-Substituted Quinolines with Vinyl Azides as a Dual Synthon via C=C and C-N Bond Cleavage
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An unprecedented Zn-promoted selective cleavage of vinyl azides for the synthesis of 4-substituted quinolines is developed. In this conversion, vinyl azides function as a dual synthon via C=C and C-N bond cleavage with two C=C bonds and one C=N bond formation in a one-step manner. The reaction is appreciated for its readily accessible substrates, high step economy, mild conditions, and use of air as the sole oxidant.
- Cen, Jinghe,Li, Jianxiao,Zhang, Yu,Zhu, Zhongzhi,Yang, Shaorong,Jiang, Huanfeng
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supporting information
p. 4434 - 4438
(2018/08/07)
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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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supporting information
p. 1065 - 1068
(2018/02/19)
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- Silver-Catalyzed Minisci Reactions Using Selectfluor as a Mild Oxidant
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A new method for silver-catalyzed Minisci reactions using Selectfluor as a mild oxidant is reported. Heteroarenes and quinones both participate in radical C-H alkylation and arylation from a variety of carboxylic and boronic acid radical precursors. Several oxidatively sensitive and highly reactive radical species are successful, providing structures that are challenging to access by other means.
- Galloway, Jordan D.,Mai, Duy N.,Baxter, Ryan D.
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supporting information
p. 5772 - 5775
(2017/11/10)
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- Preparation of 3-Iodoquinolines from N-Tosyl-2-propynylamines with Diaryliodonium Triflate and N-Iodosuccinimide
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4-Aryl and 4-alkyl substituted 3-iodoquinolines could be smoothly obtained in one pot by treating N-tosyl-2-propynylamines with diaryliodonium triflate in the presence of K3PO4 and a catalytic amount of CuCl at room temperature, followed by treatment with N-iodosuccinimide and BF3·OEt2 at 0 °C, and then NaOH in methanol solution. The product, 3-iodo-4-phenylquinoline was smoothly transformed into 4-phenylquinoline with zinc; 4-phenyl-3-toluenesulfenylquinoline with toluenethiol, K2CO3, and CuI; 4-phenyl-3-phenylethynylquinoline with the Sonogashira coupling reaction; 4-phenyl-3-styrylquinoline with the Heck coupling reaction; 3,4-diphenylquinoline with the Suzuki-Miyaura coupling reaction; 2-cyclohexyl-3-iodo-4-phenylquinoline with cyclohexanecarboxylic acid, Ag2CO3, and K2S2O8; and 3-iodo-2-(2′,5′-dioxan-1′-yl)-4-phenylquinoline with benzoyl peroxide in dioxane.
- Sasaki, Teppei,Moriyama, Katsuhiko,Togo, Hideo
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p. 11727 - 11734
(2017/11/28)
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- The one-pot synthesis of quinolines: Via Co(iii)-catalyzed C-H activation/carbonylation/cyclization of anilines
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We herein disclose a novel Co(iii)-catalyzed C-H activation/carbonylation/cyclization of anilines with ketones using paraformaldehyde as the carbonyl source, giving direct access to diverse quinolines with broad functional group tolerance and in good to excellent yields. Moreover, exclusive site-/region-selectivity was observed in this versatile transformation.
- Xu, Xuefeng,Yang, Yurong,Chen, Xin,Zhang, Xu,Yi, Wei
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supporting information
p. 9061 - 9065
(2017/11/14)
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- Carbon annulation of ortho-vinylanilines with dimethyl sulfoxide to access 4-aryl quinolines
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A palladium-catalyzed annulation of ortho-vinylanilines with dimethyl sulfoxide was developed to access 4-aryl quinolines in moderate to good yields. Activated by 1,4-diazabicyclo[2.2.2]octane bis(sulfur dioxide) adduct (DABSO), DMSO served as a “=CH-” fragment in this transformation. It represents a facile pathway leading to 4-aryl quinolines.
- Yuan, Jin,Yu, Jin-Tao,Jiang, Yan,Cheng, Jiang
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p. 1334 - 1337
(2017/02/15)
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- SILICON-BASED CROSS COUPLING AGENTS AND METHODS OF THEIR USE
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Compositions and methods using silicon-based cross-coupling agents in the formation of carbon-carbon and carbon-nitrogen bonds are described.
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Paragraph 0071
(2016/02/10)
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- Cu-Catalyzed Aerobic Oxidation of Di-tert-butyl Hydrazodicarboxylate to Di-tert-butyl Azodicarboxylate and Its Application on Dehydrogenation of 1,2,3,4-Tetrahydroquinolines under Mild Conditions
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A new class of co-catalytic system was developed with homogeneous CuI and di-tert-butyl azodicarboxylate for aerobic dehydrogenation of 1,2,3,4-tetrahydroquinolines under mild conditions. The developed co-catalytic system is consisting of di-tert-butyl azodicarboxylate-mediated dehydrogenation of 1,2,3,4-tetrahydroquinoline and aerobic oxidative regeneration of di-tert-butyl azodicarboxylate from di-tert-butyl hydrazodicarboxylate using molecular oxygen as a terminal oxidant. A variety of quinolines were efficiently synthesized by the developed Cu and di-tert-butyl azodicarboxylate co-catalytic system.
- Jung, Dahyeon,Kim, Min Hye,Kim, Jinho
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supporting information
p. 6300 - 6303
(2016/12/23)
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- Lewis acid-catalyzed borono-minisci reactions of arylboronic acids and heterocycles
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A Lewis acid-catalyzed Minisci reaction between arylboronic acids and heterocycles has been developed. This radical-coupling reaction was demonstrated employing several different heterocycles as well as electron-rich arylboronic acids. Quinoline substrates afforded modest regioselectivity for substitution at the 4-position under the reaction conditions, in contrast to previously reported Br?nsted acid-mediated reactions with quinoline substrates that favored substitution at the 2-position.
- Biaco, Joyce L.,Jones, Savannah L.,Barker, Timothy J.
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p. 1687 - 1697
(2016/10/12)
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- Cascade reaction of propargylic alcohols with hydroxylamine hydrochloride: facile synthesis of α,β-unsaturated oximes and nitriles
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We have developed an easy and practical method for the synthesis of α,β-unsaturated oximes and nitriles from readily available propargylic alcohols with hydroxylamine hydrochloride (NH2OH·HCl) under metal-free conditions. By using or not using p-toluenesulfonyl chloride (p-TsCl) as the dehydrating promoter, the desired nitriles or oximes could be obtained, respectively via a three-step one-pot or two-step one-pot process in moderate to excellent yields with good functional group compatibility.
- Zhang, Qi,Zhang, Linjing,Tang, Chaojun,Luo, Huan,Cai, Xuediao,Chai, Yonghai
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p. 6935 - 6942
(2016/10/14)
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- A concise synthesis of quinolinium, and biquinolinium salts and biquinolines from benzylic azides and alkenes promoted by copper(II) species
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A novel copper-promoted multiple aza-[4 + 2] cycloaddition reaction of N-methyleneanilines in situ generated from benzylic azide and alkenes afforded quinolinium salts, biquinolinium salts, biquinolines or substituted quinolines depending on the substitution on the phenyl ring of benzylic azide. The reaction of para substituted benzylic azides and 2 equivalents of alkenes afforded the corresponding substituted quinolinium salts, while benzylic azides without a para substituent provided biquinolinium salts. The copper-promoted cycloaddition reaction also allows biquinoline products to be obtained from ortho-substituted benzylic azides. These reactions work well with both terminal and internal alkenes. Unsymmetrical internal alkene reactions proceed with high regioselectivity. The reaction is likely started by Lewis acidic CuII-assisted rearrangement of benzylic azide to N-methyleneaniline, followed by a [4 + 2] cycloaddition with alkene. Detailed mechanistic studies suggest that the biquinoline and biquinolinium salts are likely formed via radical processes.
- Chen, Wei-Chen,Gandeepan, Parthasarathy,Tsai, Chia-Hung,Luo, Ching-Zong,Rajamalli, Pachaiyappan,Cheng, Chien-Hong
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p. 63390 - 63397
(2016/07/19)
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- Synthesis and utility of dihydropyridine boronic esters
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When activated by an acylating agent, pyridine boronic esters react with organometallic reagents to form a dihydropyridine boronic ester. This intermediate allows access to a number of valuable substituted pyridine, dihydropyridine, and piperidine products.
- Panda, Santanu,Coffin, Aaron,Nguyen, Q. Nhu,Tantillo, Dean J.,Ready, Joseph M.
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supporting information
p. 2205 - 2209
(2016/02/18)
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- Design, Synthesis, and Validation of an Effective, Reusable Silicon-Based Transfer Agent for Room-Temperature Pd-Catalyzed Cross-Coupling Reactions of Aryl and Heteroaryl Chlorides with Readily Available Aryl Lithium Reagents
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A reusable silicon-based transfer agent (1) has been designed, synthesized, and validated for effective room-temperature palladium-catalyzed cross-coupling reactions (CCRs) of aryl and heteroaryl chlorides with readily accessible aryl lithium reagents. The crystalline, bench-stable siloxane transfer agent (1) is easily prepared via a one-step protocol. Importantly, this green CCR protocol circumvents prefunctionalization, isolation of organometallic cross-coupling partners, and/or stoichiometric waste aside from LiCl. DFT calculations support a σ-bond metathesis mechanism during transmetalation and lead to insights on the importance of the CF3 groups.
- Martinez-Solorio, Dionicio,Melillo, Bruno,Sanchez, Luis,Liang, Yong,Lam, Erwin,Houk,Smith, Amos B.
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p. 1836 - 1839
(2016/03/01)
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- Metal-free aerobic one-pot synthesis of substituted/annulated quinolines from alcohols via indirect Friedl?nder annulation
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Metal-free, operationally simple, and highly efficient one-pot aerobic process for the synthesis of functionalized/annulated quinolines is devised from easily available 2-aminobenzyl alcohol/2-aminobenzophenones and alkyl/aryl alcohols for the first time. The process involves two sequential reactions, namely in situ aerial oxidation of alcohols to the corresponding aldehydes/ketones followed by Friedl?nder annulation.
- Anand, Namrata,Koley, Suvajit,Ramulu, B. Janaki,Singh, Maya Shankar
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supporting information
p. 9570 - 9574
(2015/09/28)
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- HOTf-catalyzed intermolecular hydroamination reactions of alkenes and alkynes with anilines
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Herein, the intermolecular hydroamination of alkenes and alkynes with anilines catalyzed by HOTf under mild conditions has been developed. This reaction provides one of the simplest alkene and alkyne addition methods and is an alternative to metal-catalyzed reactions. At the same time, the intramolecular hydroamination of alkynes with anilines proceeds smoothly to obtain quinolines. We found that this strategy is efficient in building complex structures from simple starting materials in an environmentally benign fashion.
- Xu, Xuefeng,Zhang, Xu,Wang, Zhiqiang,Kong, Manman
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p. 40950 - 40952
(2015/05/20)
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- Direct Transformation of Esters into Arenes with 1,5-Bifunctional Organomagnesium Reagents
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A direct transformation of carboxylic acid esters into arenes with 1,5-bifunctional organomagnesium reagents is described. This efficient and practical method enables the one-step defunctionalization of various carboxylic acid esters to prepare benzene, anthracene, tetracene, and pentacene derivatives. A double nucleophilic addition of the 1,5-organodimagnesium reagent to the ester is followed by an immediate 1,4-elimination reaction that leads to the direct [5+1] formation of a new aromatic ring.
- Link, Achim,Fischer, Christian,Sparr, Christof
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supporting information
p. 12163 - 12166
(2015/10/12)
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- Visible-light-promoted iminyl-radical formation from Acyl oximes: A unified approach to pyridines, quinolines, and phenanthridines
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A unified strategy involving visible-light-induced iminyl-radical formation has been established for the construction of pyridines, quinolines, and phenanthridines from acyl oximes. With fac-[Ir(ppy)3] as a photoredox catalyst, the acyl oximes were converted by 1 e- reduction into iminyl radical intermediates, which then underwent intramolecular homolytic aromatic substitution (HAS) to give the N-containing arenes. These reactions proceeded with a broad range of substrates at room temperature in high yield. This strategy of visible-light-induced iminyl-radical formation was successfully applied to a five-step concise synthesis of benzo[c]phenanthridine alkaloids.
- Jiang, Heng,An, Xiaode,Tong, Kun,Zheng, Tianyi,Zhang, Yan,Yu, Shouyun
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supporting information
p. 4055 - 4059
(2015/03/30)
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- Visible-light-promoted and one-pot synthesis of phenanthridines and quinolines from aldehydes and o -Acyl hydroxylamine
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A one-pot synthesis of phenanthridines and quinolines from commercially available or easily prepared aldehydes has been reported. O-(4-Cyanobenzoyl)hydroxylamine was utilized as the nitrogen source to generate O-acyl oximes in situ with aldehydes catalyzed by Bronsted acid. O-Acyl oximes were then subjected to visible light photoredox catalyzed cyclization via iminyl radicals to furnish aza-arenes. A variety of phenanthridines and quinolines have been prepared assisted by Bronsted acid and photocatalyst under visible light at room temperature with satisfactory yields.
- An, Xiao-De,Yu, Shouyun
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supporting information
p. 2692 - 2695
(2015/06/16)
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- Direct Synthesis of Nitriles from Aldehydes Using an O-Benzoyl Hydroxylamine (BHA) as the Nitrogen Source
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The direct synthesis of nitriles from commercially available or easily prepared aldehydes has been achieved. O-(4-CF3-benzoyl)-hydroxylamine (CF3-BHA) was utilized as the nitrogen source to generate O-acyl oximes in situ with aldehydes, which can be converted to a nitrile with the assistance of a Bronsted acid. Several aliphatic, aromatic, and α,β-unsaturated nitriles that contain different functional groups were prepared in high yields (up to 94% yield). This method has notable advantages, such as simple and mild conditions, high yields, and good functional group tolerance.
- An, Xiao-De,Yu, Shouyun
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p. 5064 - 5067
(2015/11/03)
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- Silver-catalyzed oxidative coupling of aniline and ene carbonyl/acetylenic carbonyl compounds: An efficient route for the synthesis of quinolines
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An efficient silver-mediated coupling of aniline with ene carbonyl/acetylenic carbonyl compounds for the synthesis of quinolines is reported. The transformation is effective for a broad range of substrates, thus enabling the expansion of substituent architectures on the heterocyclic framework. The electronic properties of the substituents on the amine have been investigated. It was found that molecules with both electron-donating and electron-withdrawing substituents were suitable substrates for this transformation, and the expected products were obtained in moderate to excellent yields. The use of a single catalytic system to mediate chemical transformations in a synthetic operation is important for the development of new atom-economic strategies and this strategy is efficient in building complex structures from simple starting materials in an environmentally benign fashion.
- Zhang, Xu,Xu, Xuefeng
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supporting information
p. 3089 - 3093
(2015/02/19)
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- Modular o-quinone catalyst system for dehydrogenation of tetrahydroquinolines under ambient conditions
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Quinolines are common pharmacophores present in numerous FDA-approved pharmaceuticals and other bioactive compounds. Here, we report the design and development of new o-quinone-based catalysts for the oxidative dehydrogenation of tetrahydroquinolines to afford quinolines. Use of a Co(salophen) cocatalyst allows the reaction to proceed efficiently with ambient air at room temperature. The utility of the catalytic method is demonstrated in the preparation of a number of medicinally relevant quinolines.
- Wendlandt, Alison E.,Stahl, Shannon S.
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supporting information
p. 11910 - 11913
(2014/10/16)
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- PLATINUM COMPOUNDS, COMPOSITIONS AND METHODS FOR THE TREATMENT OF CANCER
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The present disclosure relates to novel pharmaceutical compositions comprising a nanoparticle associated with, tether to, or encapsulating a platinum-based active pharmaceutical agent. The platinum-based drug is released from the nanoparticles in a controlled fashion. Also contemplated are methods of making the nanoparticles, as well as methods for using them in the treatment or prevention of diseases or conditions. One embodiment relates to phenanthriplatin nanoparticles and methods of using and making the same.
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Paragraph 00229
(2014/04/03)
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- Synthesis of quinolines from N-tosyl-1-azadienes
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A route to aryl-substituted quinolines from N-tosyl 1-azadienes is described. The key steps are a [4 + 2] cycloaddition with benzyne followed by base treatment of the 1,4-dihydroquinoline product. The N-tosyl 1-azadienes were prepared from readily accessible cinnamaldehyde and chalcone substrates by condensation with p-TsNH2. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications to view the free supplemental file.
- Stokes, Sean,Mead, Keith T.
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p. 2627 - 2633
(2013/07/26)
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