- Aryl-Diadamantyl Phosphine Ligands in Palladium-Catalyzed Cross-Coupling Reactions: Synthesis, Structural Analysis, and Application
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Synthesis, temperature-dependent NMR structure investigation and utilization of a new, stable and easily accessible aryl-diadamantylphosphine ligand family is reported. The bulky and electron-rich phosphorus center of the ligand enhances the catalytic activity of palladium in cross-coupling reactions of sterically demanding ortho-substituted aryl halides. In our study, we demonstrated the synthetic applicability of the new phosphine ligands in Buchwald-Hartwig and tosyl hydrazone coupling reactions.
- Sinai, ádám,Simkó, Dániel Cs.,Szabó, Fruzsina,Paczal, Attila,Gáti, Tamás,Bényei, Attila,Novák, Zoltán,Kotschy, András
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supporting information
p. 1122 - 1128
(2020/03/03)
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- Synthesis of quinoline derivatives from anilines and aldehydes catalyzed by Cp2ZrCl2 and recyclable Cp2ZrCl2/MCM-41 system
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A facile method for the synthesis of quinoline derivatives using catalytic amount of Cp2ZrCl2 or Cp2ZrCl2 supported on MCM-41 (Cp2ZrCl2/MCM-41) in reaction of anilines and aldehydes is described. When Cp2ZrCl2/MCM-41 was used as catalyst, the yields of quinolines were enhanced by 5-15% compared with Cp2ZrCl2 as catalyst alone under the same reaction conditions. More importantly, Cp2ZrCl2/MCM-41 catalyst can be reused at least thrice by simple recover via filtration in air. Moreover, both Cp2ZrCl2 and Cp2ZrCl2/MCM-41 showed good catalytic activities to generate corresponding quinoline derivatives in moderate to good yields by varying the substituent of aniline and aldehyde. And the reaction conditions were optimized by studying the influences of reactant ratio, additives, solvent effect and reaction temperatures.
- Guo, Qiaoxia,Liao, Lijun,Teng, Weiling,Ren, Shenyong,Wang, Xiao,Lin, Yingying,Meng, Fanfang
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p. 117 - 122
(2016/02/03)
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- Thiol activated prodrugs of sulfur dioxide (SO2) as MRSA inhibitors
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Drug resistant infections are becoming common worldwide and new strategies for drug development are necessary. Here, we report the synthesis and evaluation of 2,4-dinitrophenylsulfonamides, which are donors of sulfur dioxide (SO2), a reactive sulfur species, as methicillin-resistant Staphylococcus aureus (MRSA) inhibitors. N-(3-Methoxyphenyl)-2,4-dinitro-N-(prop-2-yn-1-yl)benzenesulfonamide (5e) was found to have excellent in vitro MRSA inhibitory potency. This compound is cell permeable and treatment of MRSA cells with 5e depleted intracellular thiols and enhanced oxidative species both results consistent with a mechanism involving thiol activation to produce SO2.
- Pardeshi, Kundansingh A.,Malwal, Satish R.,Banerjee, Ankita,Lahiri, Surobhi,Rangarajan, Radha,Chakrapani, Harinath
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p. 2694 - 2697
(2015/06/08)
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- Development of Quinoline-2,4(1H,3H)-diones as Potent and Selective Ligands of the Cannabinoid Type 2 Receptor
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The cannabinoid type 2 receptors (CB2Rs) play crucial roles in inflammatory diseases. There has been considerable interest in developing potent and selective ligands for CB2R. In this study, quinoline-2,4(1H,3H)-dione analogs have been designed, synthesized, and evaluated for their potencies and binding properties toward the cannabinoid type 1 receptor (CB1R) and CB2R. C5- or C8-substituted quinoline-2,4(1H,3H)-diones demonstrate CB2R agonist activity, while the C6- or C7-substituted analogs are antagonists of CB2R. In addition, oral administration of 21 dose-dependently alleviates the clinical symptoms of experimental autoimmune encephalomyelitis in a mouse model of multiple sclerosis and protects the central nervous system from immune damage. Furthermore, the interaction modes predicted by docking simulations and the 3D-QSAR model generated with CoMFA may offer guidance for further design and modification of CB2R modulators.
- Han, Shuang,Zhang, Fei-Fei,Qian, Hai-Yan,Chen, Li-Li,Pu, Jian-Bin,Xie, Xin,Chen, Jian-Zhong
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p. 5751 - 5769
(2015/08/24)
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- Use of primary amines for the selective n-alkylation of anilines by a reusable heterogeneous catalyst
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Traditionally, anilines can be alkylated with reactive alkyl halides but now more safe reagents such as alcohols or even amines can be used. To overcome the limits of homogeneous catalysis for aniline N-alkylation, we have developed a protocol that employs simple Pd/C as a heterogeneous catalyst under microwave dielectric heating. The process, based on the easy Pd-mediated oxidation of primary amines to imines followed by aniline addition, is characterized by a high atom economy as ammonia is the only other product of the reaction. This kind of aniline alkylation with amines has been carried out both in ionic liquid medium using [bmim]PF6 or in a more traditional solvent such as THF where the catalyst could be successfully recycled more times. The reusability of the catalyst was further confirmed by using material recycled from the amination in a standard alkene hydrogenation without loss of efficiency. Georg Thieme Verlag Stuttgart New York.
- Linciano, Pasquale,Pizzetti, Marianna,Porcheddu, Andrea,Taddei, Maurizio
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p. 2249 - 2254
(2013/11/06)
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- A recyclable Cu-catalyzed C-N coupling reaction in water and its application to synthesis of imidazo[1,2-a]quinoxaline
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Polystyrene-supported pyrrole-2-carbohydrazide (PSP) was synthesized and combined with CuI to make up a recyclable heterogeneous catalytic system for Ullmann-type C-N coupling reaction in water. In which, a variety of functionalized aryl halides animated efficiently with anilines, benzylamine, aliphatic amines, and imidazole. its preliminary application resulted in a more practical synthesis of imidazo[1,2-a]quinoxaline.
- Huang, Liye,Yu, Ruina,Zhu, Xinhai,Wan, Yiqian
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supporting information
p. 8974 - 8977
(2013/09/23)
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- Cobalt-catalyzed electrophilic amination of arylzincs with N-chloroamines
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Roles reversed: An efficient cobalt-catalyzed electrophilic amination of arylzinc reagents has been achieved. A variety of functionalized arylzincs and N-chloroamines were coupled under mild conditions (see scheme). Both secondary and tertiary arylamines were obtained in moderate to excellent yields. Copyright
- Qian, Xin,Yu, Zailu,Auffrant, Audrey,Gosmini, Corinne
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supporting information
p. 6225 - 6229
(2013/07/05)
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- Copper(I)-catalyzed N-arylation of N1,N3- dibenzylmalonamide and N1,N3-dibutylmalonamide followed by cleavage of the malonyl group with aryl halides under ligand-free conditions
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We primarily developed a practical and convenient protocol to synthesize of aromatic amines based on CuI-catalyzed N-arylation of N1,N 3-dibenzylmalonamide and N1,N3- dibutylmalonamide followed by cleavage of the malonyl group with aryl halides under ligand-free conditions giving good yields.
- Zheng,Xu,Shi,Ren,Lu,Zhou
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p. 1117 - 1122
(2013/05/08)
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- Copper-mediated aryl amination: In situ generation of an active copper(I) species
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We have developed novel conditions for copper-mediated aryl amination by using a combination of easy-to-handle and inexpensive Cu(OAc) 2·H2O and phenylhydrazine. Georg Thieme Verlag Stuttgart . New York.
- Komori, Takashi,Satoh, Nobuhiro,Yokoshima, Satoshi,Fukuyama, Tohru
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experimental part
p. 1859 - 1862
(2011/09/15)
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- A mild inter- and intramolecular amination of aryl halides with a combination of CuI and CsOAc
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A unique combination of CuI and CsOAc was found to catalyze aryl amination under mild conditions. The reaction takes place at room temperature or at 90 °C with broad functional group compatibility. The intramolecular reaction was able to form five-, six-, and seven-membered rings with various protecting groups on the nitrogen atom. The scope of the intermolecular amination, as well as its applications to unsymmetrical N,N′-dialkylated phenylenediamines, was investigated.
- Kubo, Tetsuji,Katoh, Chiharu,Yamada, Ken,Okano, Kentaro,Tokuyama, Hidetoshi,Fukuyama, Tohru
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experimental part
p. 11230 - 11236
(2009/04/11)
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- One-pot reductive mono-N-alkylation of aniline and nitroarene derivatives using aldehydes
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(Chemical Equation Presented) One-pot reductive mono-N-alkylation of aniline and nitroarene derivatives using various aldehydes by Pd/C catalyst in aqueous 2-propanol solvent with ammonium formate as in situ hydrogen donor is illustrated. The reaction proceeded smoothly and selectively with excellent yield at room temperature. Our protocol presents a facile, economical, and environmentally benign alternative for reductive amination.
- Byun, Eunyoung,Hong, Bomi,De Castro, Kathlia A.,Lim, Minkyung,Rhee, Hakjune
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p. 9815 - 9817
(2008/03/27)
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- Synthesis of bulky and electron-rich MOP-type ligands and their applications in palladium-catalyzed C-N bond formation
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A series of 2-dialkylphosphino-2′-alkoxy-1,1′-binaphthyl ligands (6a-c and 8a-c) have been prepared conveniently by a lithium-initiated ring-opening reaction of dinaphthofuran, followed by selective phosphorylation. These compounds displayed a remarkable air and moisture stability, both in solid form and in solution. Application of these phosphine ligands in palladium-catalyzed C-N bond forming reactions revealed the crucial roles of the steric bulk of the substituents on the phosphorus atom governing the catalytic activity. Specifically, 2-di-tert-butylphosphino-2′-isopropoxy-1,1′- binaphthyl (8b) proved to be the most effective for the aminations of aryl halides with primary amines, while the less bulky 2-dicyclohexyl-2′- methoxy-1,1′-binaphthyl (6a) was more effective for the aminations with secondary amines. The steric and electronic effects of the ligands were analyzed to account for these observations.
- Xie, Xiaomin,Zhang, Tony Y.,Zhang, Zhaoguo
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p. 6522 - 6529
(2007/10/03)
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- Reductive monoalkylation of aromatic and aliphatic nitro compounds and the corresponding amines with nitriles
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(Chemical Equation Presented) A simple, selective, rapid, and efficient procedure for the synthesis of secondary amines from the reductive alkylation of either aliphatic or aromatic nitro compounds and the corresponding amines is reported. Ammonium formate is used as the hydrogen source and Pd/C as the hydrogen transfer catalyst. The reaction is carried out at room temperature. The rate differences for the preferential formation of secondary over tertiary products are due to both steric and electronic factors.
- Nacario, Ruel,Kotakonda, Shailaja,Fouchard, David M. D.,Tillekeratne, L. M. Viranga,Hudson, Richard A.
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p. 471 - 474
(2007/10/03)
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- Synthesis of Secondary Arylamines through Copper-Mediated Intermolecular Aryl Amination
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(Equation presented) A mild intermolecular copper-mediated amination of aryl iodides has been developed. The reaction takes place at room temperature or heating at 90°C and tolerates halogens attached to the aromatic ring. Its synthetic applications include a synthetic protocol for unsymmetrical N,N′-dialkylated phenylenediamines and both a stepwise and a general synthetic method for N-aryl secondary amines via Ns-anilides (readily obtained by reaction of the Ns-amide).
- Okano, Kentaro,Tokuyama, Hidetoshi,Fukuyama, Tohru
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p. 4987 - 4990
(2007/10/03)
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- Cupric acetate mediated N-arylation by arylboronic acids: A preliminary investigation into the scope of application
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A range of NH substrates of varying nucleophilicity were reacted with a selection of electronically diverse aryl boronic acids in the presence of cupric acetate in order to evaluate the generality of a previously described N-arylation procedure. The results of that investigation are discussed.
- Cundy, Darren J.,Forsyth, Stewart A.
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p. 7979 - 7982
(2007/10/03)
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- A Facile One-pot Method for the Preparation of N-Alkylanilines
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N-Substituted anilines have been prepared by reaction of the parent anilines with butyllithium and alkyl halides.
- Vitale, Arturo A.,Chiocconi, Alejandro A.
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p. 336 - 337
(2007/10/03)
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- Ruthenium-Catalyzed N-Alkylation and N-Benzylation of Aminoarenes with Alkohols
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Aminoarenes were readily converted into secondary and tertiary amines by the reaction at 150-180 deg C with primary alcohols in the presence of a catalytic amount (1 mol percent based on the aminoarene) of a ruthenium complex.Dichlorotris(triphenylphosphine)ruthenium was the most effective catalyst precursor.Secondary amines were obtained in excellent yields when aminoarenes reacted with an equimolar amount of alcohols.With excess alcohols, tertiary amines were obtained predominantly.Kinetic measurements revealed that the rate had zero-order dependence on aminoarene concentration and first-order dependence on alcohol concentration and initial concentration of the ruthenium catalyst.From the kinetic features, the possible catalytic cycle, which includes the nucleophilic attack of the aminoarene on aldehyde intermediate, was postulated.
- Watanabe, Yoshihisa,Tsuji, Yasushi,Ige, Hitoshi,Ohsugi, Yukihiro,Ohta, Tetsuo
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p. 3359 - 3363
(2007/10/02)
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