- SmI2-mediated C-alkylation of Ketones with Alcohols under Microwave Conditions: A Novel Route to Alkylated Ketones
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A novel protocol is developed towards the preparation of alkylated ketones from alcohols in presence of catalytic amount of SmI2 and base with the elimination of water as a single by-product under microwave irradiation conditions. Furthermore, applicability of this methodology to the synthesis of Donepezil and late-stage functionalization in Pregnenolone is also reported. Successful application of this methodology in Friedl?nder quinolone synthesis using 2-aminobenzyl alcohol and various acetophenones expand the synthetic utility of this protocol.
- Gour, Jitendra,Kar, Swayamsiddha,Mahammad Ghouse, Shaik,Manohar Chelli, Sai,Nanduri, Srinivas,Pawar, Gaurav,Reddy Dannarm, Srinivas,Sonti, Rajesh
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- NiH-Catalyzed Hydroamination/Cyclization Cascade: Rapid Access to Quinolines
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Despite the significant success of metal-H-catalyzed hydroamination methodologies, considerable limitations still exist in the selective hydroamination of alkynes, especially for terminal alkynes. Herein, we develop a highly efficient NiH catalytic system that activates readily available alkynes for a cascade hydroamination/cyclization reaction with anthranils. This mild, operationally simple protocol is amenable to a wide array of alkynes including terminal and internal, aryl and alkyl, electron-deficient and electron-rich ones, delivering structurally diverse quinolines in useful to excellent yields (>80 examples, up to 93% yield). The utility of this procedure is exhibited in the late-stage functionalization of several natural products and in the concise synthesis of an antitumor molecule graveolinine and a triplex DNA intercalator. Preliminary mechanistic experiments suggest an alkenylnickel-mediated alkyne hydroamination and an intramolecular cyclization/aromatization of putative enamine intermediates.
- Chen, Qian,Gao, Yang,Hu, Xiao-Qiang,Huo, Yanping,Li, Xianwei,Yang, Simin
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p. 7772 - 7779
(2021/06/30)
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- Mild and efficient copper-catalyzed oxidative cyclization of oximes with 2-aminobenzyl alcohols at room temperature: synthesis of polysubstituted quinolines
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A simple and efficient ligand-free Cu-catalyzed protocol for the synthesis of polysubstituted quinolinesviaoxidative cyclization of oxime acetates with 2-aminobenzyl alcohols at room temperature has been developed. The presented approach provides a new synthetic pathway leading to polysubstituted quinolines with good functional group tolerance under mild conditions. Moreover, this transformation can be applied for the preparation of quinolines on a gram scale. Oxime acetates serve as the internal oxidants in the reactions, thus making this method very attractive.
- Liu, Yan-Yun,Wei, Yang,Huang, Zhi-Hui,Liu, Yilin
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supporting information
p. 659 - 666
(2021/02/06)
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- Ruthenium complex and preparation method thereof and catalytic application
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The invention discloses a ruthenium complex and a preparation method thereof and catalytic application. The ruthenium complex is reported for the first time. Research finds that the ruthenium complexhas the activity of catalytically synthesizing quinazoline and derivatives thereof or catalytically synthesizing quinoline and derivatives thereof. When the ruthenium complex provided by the inventionis used for catalytic synthesis of quinazoline and derivatives thereof or quinoline and derivatives thereof, the ruthenium complex has the advantages of mild reaction conditions, wide substrate range, high catalytic product yield and good functional group tolerance, and is significantly superior to the prior art.
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-
Paragraph 0104-0106; 0129-0130
(2021/01/24)
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- Iron catalyzed metal-ligand cooperative approaches towards sustainable synthesis of quinolines and quinazolin-4(3H)-ones
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Herein we report simple, efficient, and economically affordable metal-ligand cooperative strategies for synthesizing quinolines and quinazolin-4(3H)-ones via dehydrogenative functionalization of alcohols. Various polysubstituted quinolines and quinazolin-4(3H)-ones were prepared in good yields via dehydrogenative coupling of readily available alcohols with ketones and 2-aminobenzamides, respectively under air using a well-defined Fe(II)-catalyst, ([FeL1Cl2] (1)) bearing a redox-active azo-aromatic pincer 2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline) (L1). Control experiments and mechanistic investigation disclose that the one-electron reduced mono-anionic species [1]? bearing an iron-stabilized azo-anion radical ligand catalyzes these reactions. Both iron and the redox-active arylazo ligand participate synergistically during the different steps of these catalytic reactions.
- Mondal, Rakesh,Chakraborty, Gargi,Guin, Amit Kumar,Pal, Subhasree,Paul, Nanda D.
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- A cobalt-catalyzed method for synthesizing quinoline and quinazoline compounds
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The present invention discloses a cobalt-catalyzed synthesis of quinoline and quinazoline compounds, by a benzene compound with amino and hydroxyl groups or benzonitrile compounds as raw materials, in the presence of a catalyst and a base by a receptor-fr
- -
-
Paragraph 0011; 0046
(2022/01/10)
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- Efficient access to quinolines and quinazolines by ruthenium complexes catalyzed acceptorless dehydrogenative coupling of 2-aminoarylmethanols with ketones and nitriles
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Treatment of N,N,O-tridentate pyrazolyl-pyridinyl-alcohol ligands, 2-(CR1R2OH)-6-[3,5-(R3)2C3HN2]C5H3N (R1 = R2 = Me, R3 = H (L1H); R1 = Me, R2 = Ph, R3 = H (L2H); R1 = R2 = Ph, R3 = H (L3H); R1 = R2 = R3 = Me (L4H)) with RuCl3?xH2O in refluxing EtOH afforded the corresponding Ru(III) complexes L2RuCl (1a-1d), which were well characterized by IR, HR-MS and X-ray single crystal structural determination. These Ru complexes showed similarly high catalytic performance for both dehydrogenative couplings of 2-aminoarylmethanols with ketones and nitriles, giving the quinolines and quinazolines in good to excellent yields. This protocol provides an atom-economical and sustainable route to access various structurally important quinoline and quinazoline derivatives by using phosphine-free ligand based Ru catalysts.
- Huo, Shuaicong,Kong, Siqi,Zeng, Guang,Feng, Qi,Hao, Zhiqiang,Han, Zhangang,Lin, Jin,Lu, Guo-Liang
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- Pr2O3 Supported Nano-layered Ruthenium Catalyzed Acceptorless Dehydrogenative Synthesis of 2-Substituted Quinolines and 1,8-Naphthyridines from 2-Aminoaryl Alcohols and Ketones
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Pr2O3 supported Ru nanolayers and Ru nanoparticles catalysts were examined for the synthesis of quinolines. The Ru nanolayer was most active catalyst and showed a broad substrate scope. Structure-activity relationship demonstrated that the metallic state and morphology of Ru as well as the basic site of Pr2O3 were indispensable factors of this catalytic system.
- Chaudhari, Chandan,Sato, Katsutoshi,Ogura, Yuta,Miayahara, Shin-Ichiro,Nagaoka, Katsutoshi
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p. 2198 - 2202
(2020/03/24)
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- Synergy of anodic oxidation and cathodic reduction leads to electrochemical deoxygenative C2 arylation of quinoline: N-oxides
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The first example of electrochemical deoxygenative C2 arylation of quinoline N-oxides using sulfonyl hydrazines was demonstrated in this work. By employing both anodic oxidation and cathodic reduction, a variety of 2-arylquinolines were synthesized under metal catalyst-, exogenous-oxidant-, and exogenous-reductant-free conditions.
- Yuan, Yong,Jiang, Minbao,Wang, Tao,Xiong, Yunkui,Li, Jun,Guo, Huijiao,Lei, Aiwen
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p. 11091 - 11094
(2019/09/20)
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- Superelectrophilic Diels–Alder reactions and oxidations leading to heterocyclic biaryl compounds
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Heterocyclic imines provide biaryl products by a two-step transformation. The first transformation involves a Diels–Alder reaction with a multiply protonated imine to give a tetrahydroquinoline product, whereas the second step involves oxidation with elem
- Vuong, Hien,Klumpp, Douglas A.
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supporting information
p. 316 - 323
(2019/01/18)
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- Dehydrogenative Synthesis of Quinolines, 2-Aminoquinolines, and Quinazolines Using Singlet Diradical Ni(II)-Catalysts
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Simple, straightforward, and atom economic methods for the synthesis of quinolines, 2-aminoquinolines, and quinazolines via biomimetic dehydrogenative condensation/coupling reactions, catalyzed by well-defined inexpensive and easy to prepare singlet diradical Ni(II)-catalysts featuring two antiferromagnetically coupled singlet diradical diamine type ligands are described. Various polysubstituted quinolines, 2-aminoquinolines, and quinazolines were synthesized in moderate to good yields from different low-cost and readily accessible starting materials. Several control experiments were carried out to get insight into the reaction mechanism which shows that the nickel and the coordinated diamine ligands participate in a synergistic way during the dehydrogenation of alcohols.
- Chakraborty, Gargi,Sikari, Rina,Das, Siuli,Mondal, Rakesh,Sinha, Suman,Banerjee, Seemika,Paul, Nanda D.
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p. 2626 - 2641
(2019/02/26)
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- Metal-Ligand Cooperative Approach to Achieve Dehydrogenative Functionalization of Alcohols to Quinolines and Quinazolin-4(3 H)-ones under Mild Aerobic Conditions
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A simple metal-ligand cooperative approach for the dehydrogenative functionalization of alcohols to various substituted quinolines and quinazolin-4(3H)-ones under relatively mild reaction conditions (≤90 °C) is reported. Simple and easy-to-prepare air-stable Cu(II) complexes featuring redox-active azo-aromatic scaffolds, 2-arylazo-(1,10-phenanthroline) (L1,2), are used as catalyst. A wide variety of substituted quinolines and quinazolin-4(3H)-ones were synthesized in moderate to good isolated yields via dehydrogenative coupling reactions of various inexpensive and easily available starting materials under aerobic conditions. A few control experiments and deuterium labeling studies were carried out to understand the mechanism of the dehydrogenative coupling reactions, which indicate that both copper and the coordinated azo-aromatic ligand participate in a cooperative manner during the catalytic cycle.
- Das, Siuli,Sinha, Suman,Samanta, Deepannita,Mondal, Rakesh,Chakraborty, Gargi,Branda?, Paula,Paul, Nanda D.
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p. 10160 - 10171
(2019/08/20)
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- Nickel-Catalyzed Alkylation of Ketone Enolates: Synthesis of Monoselective Linear Ketones
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Herein we have developed a Ni-catalyzed protocol for the synthesis of linear ketones. Aryl, alkyl, and heteroaryl ketones as well as alcohols yielded the monoselective ketones in up to 90% yield. The catalytic protocol was successfully applied in to a gram-scale synthesis. For a practical utility, applications of a steroid derivative, oleyl alcohol, and naproxen alcohol were employed. Preliminary catalytic investigations involving the isolation of a Ni intermediate and defined Ni-H species as well as a series of deuterium-labeling experiments were performed.
- Das, Jagadish,Vellakkaran, Mari,Banerjee, Debasis
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p. 769 - 779
(2019/01/24)
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- Enantioselective synthesis of tunable chiral pyridine-aminophosphine ligands and their applications in asymmetric hydrogenation
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A small library of tunable chiral pyridine-aminophosphine ligands were enantioselectively synthesized based on chiral 2-(pyridin-2-yl)-substituted 1,2,3,4-tetrahydroquinoline scaffolds, which were obtained in high yields and with excellent enantioselectivities via ruthenium-catalyzed asymmetric hydrogenation of 2-(pyridin-2-yl)quinolines. The protocol features a wide substrate scope and mild reaction conditions, enabling scalable synthesis. These chiral P,N ligands were successfully applied in the Ir-catalyzed asymmetric hydrogenation of benchmark olefins and challenging seven-membered cyclic imines including benzazepines and benzodiazepines. Excellent enantio- and diastereoselectivity (up to 99% ee and >20:1 dr), and/or unprecedented chemoselectivity were obtained in the asymmetric hydrogenation of 2,4-diaryl-3H-benzo[b]azepines and 2,4-diaryl-3H-benzo[b][1,4]diazepines.
- Liu, Youran,Chen, Fei,He, Yan-Mei,Li, Chenghao,Fan, Qing-Hua
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supporting information
p. 5099 - 5105
(2019/05/29)
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- Reaction condition controlled nickel(ii)-catalyzed C-C cross-coupling of alcohols
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The challenge in the C-C cross-coupling of secondary and primary alcohols using acceptorless dehydrogenation coupling (ADC) is the difficulty in accurately controlling product selectivities. Herein, we report a controlled approach to a diverse range of β-alkylated secondary alcohols, α-alkylated ketones and α,β-unsaturated ketones using the ADC methodology employing a Ni(ii) 4,6-dimethylpyrimidine-2-thiolate cluster catalyst under different reaction conditions. This catalyst could tolerate a wide range of substrates and exhibited a high activity for the annulation reaction of secondary alcohols with 2-aminobenzyl alcohols to yield quinolines. This work is an example of precise chemoselectivity control by careful choice of reaction conditions.
- Zhang, Meng-Juan,Li, Hong-Xi,Young, David J.,Li, Hai-Yan,Lang, Jian-Ping
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supporting information
p. 3567 - 3574
(2019/04/14)
-
- 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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- A nickel catalyzed acceptorless dehydrogenative approach to quinolines
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A general, efficient and environmentally benign, one-step synthesis of substituted quinoline derivatives was achieved by acceptorless dehydrogenative coupling of o-aminobenzylalcohols with ketones and secondary alcohols catalyzed by a cheap, earth abundant and easy to prepare nickel catalyst [Ni(MeTAA)], featuring a tetraaza macrocyclic ligand (tetramethyltetraaza[14]annulene (MeTAA)). A wide variety of substituted quinolines were synthesized in high yields starting from readily available o-aminobenzylalcohols and ketones or secondary alcohols. A few controlled reactions were carried out to establish the acceptorless dehydrogenative nature of the reactions.
- Parua, Seuli,Sikari, Rina,Sinha, Suman,Das, Siuli,Chakraborty, Gargi,Paul, Nanda D.
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p. 274 - 284
(2018/01/12)
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- Synthesis of Polysubstituted Quinolines from α-2-Aminoaryl Alcohols Via Nickel-Catalyzed Dehydrogenative Coupling
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This study reports a nickel-catalyzed sustainable synthesis of polysubstituted quinolines from α-2-aminoaryl alcohols by a sequential dehydrogenation and condensation process that offers the advantages of a low catalyst loading and wide substrate scope. In contrast to earlier reported methods, this strategy allows the use of both primary as well as secondary α-2-aminoaryl alcohols in combination with either ketones or secondary alcohols for desired product formation. Using this methodology, 30 substituted quinoline derivatives were synthesized with up to 93% isolated yields.
- Das, Sanju,Maiti, Debabrata,De Sarkar, Suman
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p. 2309 - 2316
(2018/02/23)
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- A nitrogen-ligated nickel-catalyst enables selective intermolecular cyclisation of β- And γ-amino alcohols with ketones: Access to five and six-membered N-heterocycles
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Owing to the great demand for the synthesis of N-heterocycles, development of new reactions that utilise renewable resources and convert them into key chemicals using non-precious base metal-catalysts is highly desirable. Herein, we demonstrated a sustainable Ni-catalysed dehydrogenative approach for the synthesis of pyrroles, pyridines, and quinolines by the reaction of β- and γ-amino alcohols with ketones via C-N and C-C bond formations in a tandem fashion. A variety of aryl, hetero-aryl, and alkyl ketones having free amine, halide, alkyl, alkoxy, alkene, activated benzyl, and pyridine moieties were converted into synthetically interesting 2,3 and 2,3,5-substituted bicyclic as well as tricyclic N-heterocycles with up to 90% yields. As a highlight, we demonstrated the synthesis of an interesting pyrrole derivative by intermolecular cyclisation of a steroid hormone with phenylalaninol.
- Singh, Khushboo,Vellakkaran, Mari,Banerjee, Debasis
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supporting information
p. 2250 - 2256
(2018/05/30)
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- A Novel Route to 2-Arylquinolines: Reductive Cleavage of 2′-Nitroaryl-Δ2 -isoxazolines
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A novel synthetic route for the synthesis of quinolines starting from Δ 2 -isoxazolines under reductive conditions is reported. The reductive cyclization to quinolines is achieved under both metal and metal-free conditions. The reaction proceeds via an intramolecular N-H?O hydrogen bond intermediate, accelerating the reductive cleavage 1000-fold (DFT calculations) in comparison with non-hydrogen bonded system.
- Kamath, Prashantha,Viner, Russell C.,Smith, Stephen C.,Lal, Mukul
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p. 1341 - 1345
(2017/06/27)
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- Cobalt-Catalyzed α-Alkylation of Ketones with Primary Alcohols
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An ionic cobalt-PNP complex is developed for the efficient α-alkylation of ketones with primary alcohols for the first time. A broad range of ketone and alcohol substrates were employed, leading to the isolation of alkylated ketones with yields up to 98%. The method was successfully applied to the greener synthesis of quinoline derivatives while using 2-aminobenzyl alcohol as an alkylating reagent.
- Zhang, Guoqi,Wu, Jing,Zeng, Haisu,Zhang, Shu,Yin, Zhiwei,Zheng, Shengping
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supporting information
p. 1080 - 1083
(2017/03/14)
-
- Application of Off-Rate Screening in the Identification of Novel Pan-Isoform Inhibitors of Pyruvate Dehydrogenase Kinase
-
Libraries of nonpurified resorcinol amide derivatives were screened by surface plasmon resonance (SPR) to determine the binding dissociation constant (off-rate, kd) for compounds binding to the pyruvate dehydrogenase kinase (PDHK) enzyme. Parallel off-rate measurements against HSP90 and application of structure-based drug design enabled rapid hit to lead progression in a program to identify pan-isoform ATP-competitive inhibitors of PDHK. Lead optimization identified selective sub-100-nM inhibitors of the enzyme which significantly reduced phosphorylation of the E1α subunit in the PC3 cancer cell line in vitro.
- Brough, Paul A.,Baker, Lisa,Bedford, Simon,Brown, Kirsten,Chavda, Seema,Chell, Victoria,D’Alessandro, Jalanie,Davies, Nicholas G. M.,Davis, Ben,Le Strat, Loic,Macias, Alba T.,Maddox, Daniel,Mahon, Patrick C.,Massey, Andrew J.,Matassova, Natalia,McKenna, Sean,Meissner, Johannes W. G.,Moore, Jonathan D.,Murray, James B.,Northfield, Christopher J.,Parry, Charles,Parsons, Rachel,Roughley, Stephen D.,Shaw, Terry,Simmonite, Heather,Stokes, Stephen,Surgenor, Allan,Stefaniak, Emma,Robertson, Alan,Wang, Yikang,Webb, Paul,Whitehead, Neil,Wood, Mike
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supporting information
p. 2271 - 2286
(2017/04/03)
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- An efficient synthesis of quinolines via copper-catalyzed C-N cleavage
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An efficient method to synthesize substituted quinolines from ketones and 2-amino benzylamines is described. Copper-catalyzed C-N cleavage of amines followed by condensation with ketones deliver quinolines in moderate to high yields. The broad scope of su
- Xi, Long-Yi,Zhang, Ruo-Yi,Zhang, Lei,Chen, Shan-Yong,Yu, Xiao-Qi
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p. 3924 - 3930
(2015/03/30)
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- TETRAHYDROISOQUINOLINE COMPOUNDS AND THEIR USE AS PYRUVATE DEHYDROGENASE KINASE INHIBITORS
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A compound of formula (I): or a pharmaceutically acceptable salt thereof, wherein: R1 is H, Cl, F, CH3 or CF3; R2 is H, C1-C6 alkyl or optionally substituted heteroaryl or optionally substituted aryl; and R3 is (Alk)n-Rn-(Alk)n-Rn-(Alk)n-X. The compounds are useful as tetrahydroisoquinoline (THQ) compounds, which are suitable for use as PDK inhibitors, for example for inhibition of cancer cell proliferation.
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Page/Page column 144; 145
(2015/04/15)
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- Deproto-metallation using mixed lithium-zinc and lithium-copper bases and computed CH acidity of 2-substituted quinolines
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2-Substituted quinolines were synthesized, and their deproto-metallation using the bases prepared by mixing LiTMP with either ZnCl2TMEDA (1/3 equiv.) or CuCl (1/2 equiv.) was studied. With phenyl and 2-naphthyl substituents, the reaction occurred at the 8 position of the quinoline ring, affording the corresponding iodo derivatives or 2-chlorophenyl ketones using the lithium-zinc or the lithium-copper combination, respectively. With a 4-anisyl substituent, a dideprotonation at the 8 and 3′ position was noted using the lithium-zinc base. With 3-pyridyl, 2-furyl and 2-thienyl substituents, the reaction took place on the substituent, at a position adjacent to its heteroatom. 2-Chlorophenyl-2-phenyl-8-quinolyl ketone could be cyclized under palladium catalysis. The experimental results were analyzed with the help of the CH acidities of the substrates, determined in THF solution using the DFT B3LYP method.
- Marquise, Nada,Bretel, Guillaume,Lassagne, Frederic,Chevallier, Floris,Roisnel, Thierry,Dorcet, Vincent,Halauko, Yury S.,Ivashkevich, Oleg A.,Matulis, Vadim E.,Gros, Philippe C.,Mongin, Florence
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p. 19602 - 19612
(2014/05/20)
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- Tetraphosphine/palladium-catalyzed Suzuki-Miyaura coupling of heteroaryl halides with 3-pyridine- and 3-thiopheneboronic acid: An efficient catalyst for the formation of biheteroaryls
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An easily prepared tetraphosphine N,N,N′,N′- tetra(diphenylphosphinomethyl)-1,2-ethylenediamine (L1) associated with [Pd(η3-C3H5)Cl]2 affords an efficient catalyst for Suzuki-Miyaura coupling of 3-pyridineboronic acid with heteroaryl bromides. Reaction could be performed with as little as 0.02 mol% catalyst and a high turnover number of 2500 is obtained. A wide range of substrates is investigated with satisfactory yields, and good compatibility with aminogroup-substituted pyridines and unprotected indole is exhibited. This protocol can also be applied successfully to the reaction of heteroaryl bromides with 3-thiopheneboronic acid. This Pd-tetraphosphine catalyst efficiently restrains the poisoning effect from heteroaryls, and shows good stability and longevity. Copyright 2013 John Wiley & Sons, Ltd. An easily prepared tetraphosphine L1 was successfully used in Pd catalyzed Suzuki reaction of heteroaryl bromides with 3-pyridineboronic acid. A high turnover number of 2 500 was achieved and a wide range of heteroaryl halides including aminopyridines and indole was tolerated. With this protocol the coupling of 3-thiopheneboronic acid with heteroaryl bromides could also proceed in good yields. This catalyst system efficiently restrained poisoning effect from heteroaryls, and exhibited good stability and longevity. Copyright
- Wang, Kun,Fu, Qi,Zhou, Rong,Zheng, Xueli,Fu, Haiyan,Chen, Hua,Li, Ruixiang
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p. 232 - 238
(2013/05/08)
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- PdCl2(dppf)-catalyzed in situ coupling of 2-hydroxypyridines with aryl boronic acids mediated by PyBroP and the one-pot chemo- and regioselective construction of two distinct aryl-aryl bonds
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We present a PdCl2(dppf)-catalyzed synthesis of 2-arylated pyridine derivatives via the in situ coupling of 2-OH pyridines and boronic acids mediated by PyBroP. In addition, the highly chemo- and regioselective construction of two different aryl-aryl bonds via a one-pot operation has also been demonstrated by the orthogonal use of this method with the Ni-catalyzed Suzuki-Miyaura coupling of phenols.
- Li, Shui-Ming,Huang, Jie,Chen, Guo-Jun,Han, Fu-She
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supporting information; experimental part
p. 12840 - 12842
(2012/01/05)
-
- Selective reduction of nitroarenes by a Hantzsch 1,4-dihydropyridine: A facile and efficient approach to substituted quinolines
-
An efficient reductive cyclization of o-nitrocinnamoyl compounds was achieved by employing a Hantzsch 1,4-dihydropyridine ester as a biomimetic reducing agent in the presence of catalytic palladium on carbon. This approach was successfully applied to the synthesis of substituted quinolines. Georg Thieme Verlag Stuttgart ? New York.
- Xing, Rui-Guang,Li, Ya-Nan,Liu, Qiang,Han, Yi-Feng,Wei, Xia,Li, Jing,Zhou, Bo
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experimental part
p. 2066 - 2072
(2011/08/05)
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- Highly efficient suzuki-miyaura coupling of heterocyclic substrates through rational reaction design
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A dicyclohexyl(2-sulfo-9-(3-(4-sulfophenyl)propyl)-9H-fluoren-9-yl) phosphonium salt was synthesized in 64% overall yield in three steps from simple commercially available starting materials. The highly water-soluble catalyst obtained from the corresponding phosphine and [Na2PdCl4] enabled the Suzuki coupling of a broad variety of N- and S-heterocyclic substrates. Chloropyridines (-quinolines) and aryl chlorides were coupled with aryl-, pyridineor indoleboronic acids in quantitative yields in water/n-butanol solvent mixtures in the presence of 0.005-0.05 mol% of Pd catalyst at 100°C, chloropurines were quantitatively Suzuki coupled in the presence of 0.5 mol% of catalyst, and S-heterocyclic aryl chlorides and aryl- or 3-pyridylboronic acids required 0.01-0.05 mol % Pd catalyst for full conversion. The key to the high activity of the Pd-phosphine catalyst is the rational design of the reaction parameters (i.e., the presence of water in the reaction mixture, good solubility of reactants and catalyst in n-butanol/water (3:1), and the electron-rich and sterically demanding nature of the phosphine ligand).
- Fleckenstein, Christoph A.,Plenio, Herbert
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scheme or table
p. 4267 - 4279
(2009/05/07)
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- Heteroaryl-substituted naphthalenes and structurally modified derivatives: Selective inhibitors of CYP11B2 for the treatment of congestive heart failure and myocardial fibrosis
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Recently we proposed inhibition of aldosterone synthase (CYP11B2) as a novel strategy for the treatment of congestive heart failure and myocardial fibrosis. In this study the synthesis and biological evaluation of heteroaryl-substituted naphthalenes and quinolines (1-31) is described. Key step for the preparation of the compounds was a Suzuki cross-coupling. Activity of the compounds was determined in vitro using human CYP11B2 and selectivity was evaluated toward the human steroidogenic enzymes CYP11B1, CYP19, and CYP17. A large number of highly active and selective inhibitors of CYP11B2 was identified. The most active inhibitor was the 6-cyano compound 8 (IC 50 = 3 nM) showing a competitive type of inhibition (Ki value = 1.9 nM). The 6-ethoxy derivative 5 was found to be the most selective CYP11B2 inhibitor (IC50 = 12 nM; Ki value = 8 nM; CYP11B1 IC50 = 5419 nM; selectivity factor = 451), showing no inhibition of human CYP3A4 (50 nM) and CYP2D6 (20 nM). Docking and molecular dynamics studies using our homology modeled CYP11B2 structure with selected compounds were performed. Caco-2 cell experiments revealed a large number of medium and highly permeable compounds and metabolic studies with 2 using rat liver microsomes showed sufficient stability.
- Voets, Marieke,Antes, Iris,Scherer, Christiane,Müller-Vieira, Ursula,Biemel, Klaus,Barassin, Catherine,Marchais-Oberwinkler, Sandrine,Hartmann, Rolf W.
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p. 6632 - 6642
(2007/10/03)
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- Efficient catalyst for the Suzuki-Miyaura coupling of potassium aryl trifluoroborates with aryl chlorides
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Palladium-catalyzed Suzuki-Miyaura cross-coupling reactions of aryl- and heteroaryl chlorides with potassium aryl- and heteroaryltrifluoroborates have been accomplished with the supporting ligand S-Phos in good to excellent yield. Hindered biaryls and substrates containing a variety of functional groups can be prepared. Suzuki-Miyaura couplings of a 3-pyridyl boron-based nucleophile with aryl- and heteroaryl chlorides proceed in good to very good yield.
- Barder, Timothy E.,Buchwald, Stephen L.
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p. 2649 - 2652
(2007/10/03)
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- Iron catalyzed cross coupling reactions of aromatic compounds
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A process for the production of compounds Ar—R1 by means of a cross-coupling reaction of an organometallic reagent R1—M with an aromatic or heteroaromatic substrate Ar—X catalyzed by one or several iron salts or iron complexes as catalysts or pre-catalysts, present homogeneously or heterogeneously in the reaction mixture. This new invention exhibits substantial advantages over established cross coupling methodology using palladium- or nickel complexes as the catalysts. Most notable aspects are the fact that (i) expensive and/or toxic nobel metal catalysts are replaced by cheap, stable, commercially available and toxicologically benign iron salts or iron complexes as the catalysts or pre-catalysts, (ii) commercially attractive aryl chlorides as well as various aryl sulfonates can be used as starting materials, (iii) the reaction can be performed under “ligand-free” conditons, and (iv) the reaction times are usually very short.
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Page/Page column 7
(2010/02/03)
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- Iron-catalyzed cross-coupling reactions
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Simple iron salts such as FeCln, Fe(acac)n (n = 2,3) or the salen complex 4 turned out to be highly efficient, cheap, toxicologically benign, and environmentally friendly precatalysts for a host of cross-coupling reactions of alkyl o
- Fuerstner, Alois,Leitner, Andreas,Mendez, Maria,Krause, Helga
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p. 13856 - 13863
(2007/10/03)
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- Cross-coupling between 3-pyridylmagnesium chlorides and heteroaromatic halides
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Phenyl- and thienylpyridines were prepared by Pd(0)-catalyzed cross-coupling of 3-pyridylmagnesium chlorides with iodobenzene or iodothiophene at room temperature. Starting from bromo and chloro azines and diazines, the Ni(0)-catalyzed reaction proved more suitable to allow the synthesis of pyridylpyridines, pyridylquinolines and pyridyldiazines.
- Bonnet, Véronique,Mongin, Florence,Trécourt, Fran?ois,Breton, Gilles,Marsais, Francis,Knochel, Paul,Quéguiner, Guy
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p. 1008 - 1010
(2007/10/03)
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- Preparation of ?-Deficient Heteroarylzinc Halides by Oxidative Addition of Active Zinc and Its Palladium-Catalyzed Reaction
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The oxidative addition of active zinc to iodo- and bromo-substituted ?-deficient heteroarenes such as pyridine, pyrimidine, and quinoline gave the corresponding heteroarylzinc halides which were transformed to the arylated and benzoylated derivatives by palladium-catalyzed reaction.
- Sakamoto, Takao,Kondo, Yoshinori,Murata, Naoko,Yamanaka, Hiroshi
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p. 9713 - 9720
(2007/10/02)
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- PREPARATION OF PYRIDYL GRIGNARD REAGENTS AND CROSS COUPLING REACTIONS WITH SULFOXIDES BEARING AZAHETEROCYCLES
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Pyridyl Grignard reagents were prepared from the corresponding iodopyridine and EtMgBr.New cross coupling reactions of the Grignard reagents with azaheterocycles took place on the sulfinyl sulfur atom to afford biazaheteroaryls.
- Furukawa, Naomichi,Shibutani, Tadao,Fujihara, Hisashi
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p. 5845 - 5848
(2007/10/02)
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- A SIMPLE REGIOSELECTIVE PREPARATION OF 2- OR 3-SUBSTITUTED QUINOLINE DERIVATIVES VIA DIALKYLQUINOLYLBORANES
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Various quinoline derivatives possessing a substituent at the 2- or 3-position were prepared by the reaction of dialkylquinolylboranes and organic bromides in the presence of a palladium catalyst.
- Ishikura, Minoru,Oda, Izumi,Terashima, Masanao
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p. 2375 - 2386
(2007/10/02)
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