- Bis(μ-iodo)bis((-)-sparteine)dicopper(I): versatile catalyst for direct N-arylation of diverse nitrogen heterocycles with haloarenes
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The easy-to-prepare dimeric bis(μ-iodo)bis((-)-sparteine)dicopper(I) complex is shown to be a versatile catalyst for N-arylation of number of NH-heterocycles with structurally divergent aryl halides including activated aryl chloride substrates under mild conditions. The DFT studies not only provide structural insights into square-pyramidal Cu(III) intermediate complexes derived from (-)-sparteine, but also highlight the important role of sterically demanding (-)-sparteine ligand framework in promoting activation of aryl-chlorine bonds for N-arylation of imidazoles.
- Maheswaran,Krishna, G. Gopi,Prasanth, K. Leon,Srinivas,Chaitanya, G. Krishna,Bhanuprakash
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- Cheap Cu(I)/hexamethylenetetramine (HMTA) catalytic system for C-N coupling reactions
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An efficient C-N coupling reaction of aryl chlorides or bromides with imidazole was successfully performed with cheap and commercially available catalytic system Cu(I)/HMTA. Both aryl bromides and aryl chlorides have been effectively catalyzed by Cu/HMTA, giving products in moderate to good yields. Moreover, aryl halides bearing either electron-withdrawing groups or electron-donating groups could be used in the reaction. Taylor & Francis Group, LLC.
- Cao, Changsheng,Lu, Zhongbo,Cai, Zhengyuan,Pang, Guangsheng,Shi, Yanhui
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- Open-air N-arylation of N-H heterocycles with arylboronic acids catalyzed by copper(II) Schiff base complexes
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Two copper Schiff base complexes, in both homogeneous and heterogeneous forms, were prepared and characterized by using elemental analysis, FTIR, UV-Vis spectroscopy and scanning electron microscopy. The catalytic performances of these complexes were studied in the N-arylation of N-H heterocycles with arylboronic acids in methanol without any added base at 40 °C under open air. The effects of various parameters such as solvent and temperature on the reaction system were studied. The reaction is applicable to a wide variety of N-H heterocycles and arylboronic acids. The heterogeneous catalyst was recovered by simple filtration, and reusability experiments showed that this catalyst can be used five times without much loss in the catalytic activity.
- Islam,Dey, Ram Chandra,Roy, Anupam Singha,Paul, Sumantra,Mondal, Sanchita
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- A versatile and efficient cu-catalyzed N-Arylation of aromatic cyclic secondary amines with aryl halides
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A copper-catalyzed coupling reaction of aryl halides with various aromatic cyclic secondary amines in DMSO has been developed efficiently. The versatile and efficient copper catalyst system is of wide-spread and practical application in cross-coupling reactions.
- Yang, Haitao,Miao, Zhiwei,Chen, Ruyu
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- Cross coupling of arylboronic acids with imidazoles by sulfonatocopper(II) (salen) complex in water
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A mild and clean protocol for the cross coupling reactions between imidazoles and arylboronic acids has been developed in good to excellent yields up to 98% in the presence of sulfonatocopper(II)(salen) catalyst in water without addition of other additives and bases.
- Wang, Lixia,Jiang, Zhaoqiong,Yu, Lintao,Li, Lili,Li, Zhengkai,Zhou, Xiangge
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- 2,6-Bis(2-methylhydrazine-1-carbonyl)pyridine 1-oxide as an Efficient Ligand for Copper-Catalyzed C–N Coupling Reaction in Water
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Abstract: Cu2O/2,6-bis(2-methylhydrazine-1-carbonyl)pyridine 1-oxide was found to be an efficiently catalytic system for the N-arylation of imidazole, indole, benzimidazole, pyrrole, benzylamine and ethanolamine with aryl iodides and bromides by using NaOH as base in the presence of 20?mol% (n-Bu)4NBr, and water as solvent at 130?°C in 24?h, and giving the N-arylated products in moderate to excellent yields.
- Wang, Xiaochuang,Meng, Fei,Zhang, Jie,Xie, Jianwei,Dai, Bin
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- Copper(I) 3-methylsalicylate mediates the Chan-Lam N-arylation of heterocycles
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Copper(I) 3-methylsalicylate (CuMeSal) mediates N-arylation reactions between aryl boronic acids and aromatic heterocycles (Chan-Lam coupling) under moderate reaction conditions (K2CO3, methanol, 65 °C, in air, 3-5 h). Both electron-rich and electron-deficient aryl boronic acids and a diverse set of N-heterocycles were allowed to react and gave N-arylation products in reasonable yields, which demonstrate the utility of this catalyst.
- Farahat, Abdelbasset A.,Boykin, David W.
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- Cu(OTf)2-Mediated Cross-Coupling of Nitriles and N-Heterocycles with Arylboronic Acids to Generate Nitrilium and Pyridinium Products**
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Metal-catalyzed C–N cross-coupling generally forms C?N bonds by reductive elimination from metal complexes bearing covalent C- and N-ligands. We have identified a Cu-mediated C–N cross-coupling that uses a dative N-ligand in the bond-forming event, which, in contrast to conventional methods, generates reactive cationic products. Mechanistic studies suggest the process operates via transmetalation of an aryl organoboron to a CuII complex bearing neutral N-ligands, such as nitriles or N-heterocycles. Subsequent generation of a putative CuIII complex enables the oxidative C–N coupling to take place, delivering nitrilium intermediates and pyridinium products. The reaction is general for a range of N(sp) and N(sp2) precursors and can be applied to drug synthesis and late-stage N-arylation, and the limitations in the methodology are mechanistically evidenced.
- Bell, Nicola L.,Xu, Chao,Fyfe, James W. B.,Vantourout, Julien C.,Brals, Jeremy,Chabbra, Sonia,Bode, Bela E.,Cordes, David B.,Slawin, Alexandra M. Z.,McGuire, Thomas M.,Watson, Allan J. B.
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- Benzotriazole: an excellent ligand for Cu-catalyzed N-arylation of imidazoles with aryl and heteroaryl halides
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Benzotriazole (BtH) is an efficient ligand for the Cu-catalyzed N-arylation of imidazoles with aryl and heteroaryl halides. A combination of CuI/BtH was found to be an efficient and inexpensive catalyst system to carry out the N-arylation of imidazoles affording the corresponding products in good to excellent yields.
- Verma, Akhilesh Kumar,Singh, Jaspal,Sankar, V. Kasi,Chaudhary, Ritu,Chandra, Ramesh
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- An in situ generated CuI/metformin complex as a novel and efficient catalyst for C-N and C-O cross-coupling reactions
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An in situ generated complex of copper(I) and a biguanide, namely metformin, was found to be a highly efficient homogeneous catalyst in N/O-arylation reactions. The O-arylation of substituted phenols with various aryl iodides and bromides was also achieved using this copper catalyst to afford diaryl ethers in good to excellent yields in DMF. This heterogeneous copper catalyst also promotes the N-arylation of imidazole with a variety of aryl halides (Cl, Br, I) in acetonitrile.
- Ghorbani-Vaghei, Ramin,Hemmati, Saba,Veisi, Hojat
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- Copper-catalyzed C-N bond formation with N-heterocycles and aryl halides
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The microwave-assisted, cuprous oxide catalyzed coupling of aryl bromides and iodides with imidazole, benzimidazole, pyrazole, or triazole was found to give a wide range of N-aryl heteroaromatic products in good to high yields. Aryl dibromides undergo sel
- Boswell, Mikki G.,Yeung, Fanny G.,Wolf, Christian
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- Tetrazole-1-acetic acid as a ligand for copper-catalyzed N-arylation of imidazoles with aryl iodides under mild conditions
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Tetrazole-1-acetic acid was found to serve as a superior ligand for CuI-catalyzed N-arylation of imidazoles with aryl iodides under a low catalyst loading (5 mol% of CuI). A variety of aryl iodides could be aminated to provide the N-arylated products in good to excellent yields without the need of an inert atmosphere.
- Wu, Feng-Tian,Liu, Ping,Ma, Xiao-Wei,Xie, Jian-Wei,Dai, Bin
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- Expanding the Electrochemical Window: New Tunable Aryl Alkyl Ionic Liquids (TAAILs) with Dicyanamide Anions
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A set of new tunable aryl alkyl ionic liquids (TAAILs) based on the 1-aryl-3-alkyl imidazolium motif has been synthesized, in which the following variables were systematically changed: alkyl chain length, aryl substitution (group and position), and counte
- Lerch, Swantje,Strassner, Thomas
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- Immobilization of copper(II) into polyacrylonitrile fiber toward efficient and recyclable catalyst in Chan-Lam coupling reactions
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A series of polyacrylonitrile fiber (PANF)-supported copper(II) catalysts were prepared through the immobilization of Cu(II) into prolinamide-modified PANF (PANPA-2F) and subsequently used for the synthesis of diverse N-arylimidazoles from arylboronic acids and imidazole. The prepared Cu(II)@PANPA-2Fs were well characterized by mechanical strength, FT-IR, XRD, XPS and SEM. Among them, CuCl2@PANPA-2F exhibited excellent catalytic performance, and its activity was significantly affected by the Cu loading. This catalytic system also displayed good activity in the synthesis of N-arylsulfonamides from arylboronic acids and tosyl azide. It was highly efficient in gram-scale reactions and could be reused five times. The advantages of low cost, easy preparation, good durability and facile recovery make the fiber catalyst attractive.
- Zhang, Chenlu,Zhu, Hai,Gang, Kaiyue,Tao, Minli,Ma, Ning,Zhang, Wenqin
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- Methoxyaryl substituted palladium bis-NHC complexes - Synthesis and electronic effects
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A series of methoxyphenyl substituted chelated bis-N-heterocyclic carbene palladium(II) complexes has been synthesized and characterized by cyclovoltammetry, spectroscopy (NMR, IR), solid state structures and investigated by quantum chemical calculations.
- Munz, Dominik,Allolio, Christoph,D?ring, Katrin,Poethig, Alexander,Doert, Thomas,Lang, Heinrich,Stra?ner, Thomas
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- N-Arylation of nitrogen containing heterocycles with aryl halides using copper nanoparticle catalytic system
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Cu nanoparticles promoted N-arylation of NH-heterocycles with aryl halides is an effective and inexpensive method. In this synthetic protocol, good to excellent yields are obtained. Both aryl iodide and aryl bromide are compatible with the reaction conditions.
- Pai, Gita,Chattopadhyay, Asoke P.
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- Cu-doped CoFe2O4 nanoparticles as magnetically recoverable catalyst for C–N cross-coupling reaction
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A new hybrid catalyst has been developed by immobilizing copper acetate onto surface of cobalt ferrite magnetic nanoparticles bearing N–O chelating ligand. The magnetic core of the catalyst was synthesized via ultrasound assisted co-precipitation method and characterized by FT-IR, XRD, EDX, SEM, TEM, TGA and VSM analysis. The catalyst was found to be very active for C–N bond forming reaction. Coupling of amines and aryl boronic acid could be achieved in high yield in methanol in presence of triethylamine at room temperature. After completion of the reaction the catalyst could be recovered using an external magnet and reused for consecutive catalytic cycles without significant decrease in the catalytic activity.
- Dutta, Mintu Maan,Phukan, Prodeep
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- Copper(I) 3-methylsalicylate, an efficient catalyst for N-arylation of heterocycles under moderate reaction conditions
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Copper(I) 3-methylsalicylate mediates N-arylation reactions of both aliphatic and aromatic heterocycles under moderate reaction conditions. Both electron rich and electron poor aryl bromides and a diverse set of N-heterocycles were allowed to react and gave N-arylation products in high yields which demonstrated the efficiency and utility of this catalyst.
- Farahat, Abdelbasset A.,Boykin, David W.
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- Model studies of the histidine-tyrosine cross-link in cytochrome c oxidase reveal the flexible substituent effect of the imidazole moiety
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(Chemical Equation Presented) Experimental and theoretical studies were carried out to interrogate the effect of an imidazole substituent in each of the ortho, meta, and para positions on the pKa, E°, and O-H BDE of phenol. The results reveal t
- Pratt, Derek A.,Pesavento, Russell P.,Van Der Donk, Wilfred A.
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- Copper powder-catalyzed N-arylation of imidazoles in water using 2-(hydrazinecarbonyl)pyridine N-oxides as the new ligands
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2-(2-Hydrazinecarbonyl)pyridine N-oxides, which were derived from pyrrole-2-carbohydrazides and pyridine N-oxides, were synthesized and utilized as the ligands for copper powder-catalyzed N-arylation of imidazoles with aryl halides in water. Imidazoles could be arylated smoothly with various aryl halides to provide the title products in preferable yields without the need of an inert atmosphere.
- Wu, Feng-Tian,Yan, Nan-Nan,Liu, Ping,Xie, Jian-Wei,Liu, Yan,Dai, Bin
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- Formation of N-Heterocyclic Carbenes by Tautomerization of Mesomeric Betaines: Cyclic Boron Adducts and Palladium Complexes from 2-(Imidazolium-1-yl)phenolates
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2-(Imidazolium-1-yl)phenolates are conjugated heterocyclic mesomeric betaines in tautomeric equilibrium with the corresponding N-heterocyclic carbenes (NHCs), 3-(2-hydroxyphenyl)-imidazol-2-ylidenes. The carbene tautomers can be trapped as thiones (X-ray analysis). Moreover, bis(triphenylphosphine)palladium(II) dichloride in THF trapped the carbene tautomer as a palladium complex without participation of the phenolate group (X-ray analysis). The corresponding anionic NHCs, 2-phenolate-substituted imidazol-2-ylidenes, can be trapped by triethylborane or triphenylborane to form 4,4-diethyl- or 4,4-diphenyl-4H-benzo[e]imidazo[2,1-c][1,4,2]oxaza-borininium-4-ides, respectively (two X-ray analyses). These tricyclic systems are the first representatives of a new heterocyclic ring system. The results of DFT calculations concerning the HOMO/LUMO profiles and partial charges are also presented.
- Liu, Ming,Nieger, Martin,Hübner, Eike G.,Schmidt, Andreas
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- Palladium nanoparticles supported on modified single-walled carbon nanotubes: A heterogeneous and reusable catalyst in the Ullmann-type N-arylation of imidazoles and indoles
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Air- and moisture-stable and recyclable palladium nanoparticles supported on modified single-walled carbon nanotubes (SWCNT-Met/Pd) behave as very efficient heterogeneous catalysts in the Ullmann coupling of imidazoles and indoles with aryl iodides to afford the corresponding C-N coupling reactions under aerobic conditions. These cross coupled products were produced in excellent yields at low palladium loading (~0.2 mol%) and the heterogeneous catalyst can be readily recovered by simple filtration and reused five times without a noticeable loss in its catalytic activity.
- Veisi, Hojat,Morakabati, Nekoo
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- Efficient Ullmann C-X coupling reaction catalyzed by a recoverable functionalized-chitosan supported copper complex
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Three different types of functionalized-CS were prepared and anchored with copper salts for use as the catalyst for the Ullmann C-X coupling reaction. The Schiff-basic chitosan supported copper complex (PCCS@CuI) exhibits the highest catalytic activity. The structure of the catalyst was characterized by FTIR spectroscopy, TG, XRD, SEM, EDS and XPS. This catalyst exhibited high applicability for the C-N and C-S coupling reactions, in which good to excellent yields were obtained. Its easy separation, good reusability and stability were notable.
- Liu, Xuemin,Chang, Shuo,Chen, Xinzhi,Ge, Xin,Qian, Chao
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- 3-(Diphenylphosphino)propanoic acid: An efficient ligand for the Cu-catalyzed N-arylation of imidazoles and 1H-pyrazole with aryl halides
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3-(Diphenylphosphino)propanoic acid (L2) has proved to be an efficient ligand for the copper-catalyzed CN coupling reactions. N-arylation of imidazoles with aryl iodides catalyzed by CuCl/L2 was smoothly carried out in DMSO at 100 °C with a yield up to 98%. N-arylation of 1H-pyrazole with aryl iodides and bromides catalyzed by Cu(OAc)2/L2 in 1,4-dioxane also gave the corresponding products with yields of 40%-98%.
- Liu, Ya-Shuai,Liu, Yan,Ma, Xiao-Wei,Liu, Ping,Xie, Jian-Wei,Dai, Bin
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- Palladium(II) 9,10-phenanthrenequinone N-substituted thiosemicarbazone/semicarbazone complexes as efficient catalysts for N-arylation of imidazole
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A series of palladium complexes, [PdCl(L1-4)] (1-4) (L1 = 9,10-phenanthrenequinone thiosemicarbazone, L2 = 9,10-phenanthrenequinone methylthiosemicarbazone, L3 = 9,10-phenanthrenequinone phenylthiosemicarbazone, and L4 = 9,10-phenanthrenequinone semicarbazone), have been synthesized and characterized by elemental analyses, UV-vis, FT-IR, 1H and 13C NMR, and ESI-Mass spectroscopic methods. The catalytic efficiency of the synthesized complexes was examined against N-arylation of imidazole. The system works well with the electron-rich, -neutral, and -deficient aryl halides to afford the products in good to excellent yields. Sterically congested aryl halides and heteroaryl halides have also been used as substrates to provide N-arylated heterocycles. In addition, this methodology can be applicable to other substrates with N-containing heterocycles.
- Anitha, Panneerselvam,Manikandan, Rajendran,Viswanathamurthi, Periasamy
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- β-Ketoimine as an efficient ligand for copper-catalyzed N-arylation of nitrogen-containing heterocycles with aryl halides
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An efficient copper catalyst system, Cu2O/β-ketoimine L1, for the N-arylation of nitrogen-containing heterocycles with aryl iodides and bromides has been developed. The system works well with the electron-rich, -neutral, and -deficient aryl bromides to afford the products in good to excellent yields.
- Xue, Fei,Cai, Chengyi,Sun, Hongmei,Shen, Qi,Rui, Jiao
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- Efficient copper-catalyzed N-arylation of amides and imidazoles with aryl iodides
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The C-N cross-coupling of amides and imidazoles with aryl iodides is described using CuI in tetrabutylammonium bromide (TBAB) under ligand-free conditions. The reaction is simple, general, and efficient affording the C-N cross-coupled products in shorter time and in high yield. Georg Thieme Verlag Stuttgart ? New York.
- Ali, Md. Ashif,Saha, Prasenjit,Punniyamurthy, Tharmalingam
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- A designed bi-functional sugar-based surfactant: Micellar catalysis for C-X coupling reaction in water
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A bi-functional sugar-based surfactant ALA14 was designed as the ligand and micelle constructor and demonstrated to promote the copper-catalyzed C-X coupling reaction in water. The nature of this micelle, formed by sugar-based surfactants, was investigated with CMC, DLS, and TEM, by which encapsulation and aggregation of the substrates in micelles were verified. Additionally, it was addressed by 1H-NMR analysis that the enrichment position of the substrates is in the lipophilic alkyl chain. Finally, moderate to excellent yields of the aimed products were obtained in this work. This remarkably simple strategy expanded the scope of C-X coupling reaction in water; most notably, both water and ALA14 can be recycled and reused.
- Ge, Xin,Zhang, Shihui,Chen, Xinzhi,Liu, Xuemin,Qian, Chao
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- A concept of supported amino acid ionic liquids and their application in metal scavenging and heterogeneous catalysis
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Novel supported task-specific ionic liquids have been developed for the first time via the ionic-pair coupling of imidazolium cation of the modified polystyrene support with L-proline. The materials have shown an efficient metal scavenging ability (e.g., Cul, Pd(OAc)2, Pd0, and IrCl3) without the aid of a nonimmobilized ionic liquid, which relies on the highly synergistic effect of the coordination with the nitrogen atom and the COO- group of the L-proline moiety, electrostatic forces, and steric protection. The resulting metal-soaked supported ionic liquids can be used as efficient heterogeneous catalysts. These materials have been investigated in the Cul-catalyzed N-arylation of nitrogen-containing heterocycles and exhibit much higher catalytic activity and a more extensive structural range of aryl and heteroaryl halides than those exhibited by free L-proline in combination with Cul both in the ionic liquid ([BMIM][BF 4]) and in the corresponding homogeneous reaction conditions. The Cul-soaked catalyst 4a-2 can be recycled for nine runs at least without any considerable loss of activity. To the best of our knowledge, our catalytic process is among the most efficient approaches to the N-arylation of imidazoles with aryl halides so far reported. Furthermore, the Pd-soaked material 4a-2 also shows higher catalytic activity in the solvent-free hydrogenation of styrene to ethylbenzene. This new concept is generally applicable and may easily be extended to other supported task-specific ionic liquids.
- Chen, Wen,Zhang, Yuanyuan,Zhu, Liangbo,Lan, Jingbo,Xie, Rugang,You, Jingsong
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- Nickel(II) complex incorporating methylene bridged tetradentate dicarbene ligand as an efficient catalyst toward CC and CN bond formation reactions
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For the evaluation of binding and catalytic nature of N-heterocyclic carbenes (NHCs) and their complexes, a new methylene bridged bis(aryloxy-NHC) ligand has been prepared. A novel air-stable Ni(II) complex bearing the new NHC ligand has been synthesized and characterized by elemental analysis, NMR (1H and 13C) as well as ESI-mass spectrometry. The molecular structure of the complex was identified by means of single crystal X-ray diffraction analysis which revealed that the Ni(II) complex possesses a square planar geometry with the ligand coordinating with bi-negative tetradentate C2O2 fashion and the complex showed efficient catalytic activity toward the Suzuki-Miyaura cross-coupling reaction between aryl halides and arylboronic acids under phosphine free conditions. The new complex also catalyzed the amination of aryl chlorides in the presence of KOtBu. Various aryl chlorides and amines can react smoothly to give the corresponding aminated products in moderate to high yields. Both secondary and primary amines are well tolerated under the optimal reaction conditions.
- Nirmala, Muthukumaran,Prakash, Govindan,Ramachandran, Rangasamy,Viswanathamurthi, Periasamy,Malecki, Jan Grzegorz,Linert, Wolfgang
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- Chan-Lam-Type C-N Cross-Coupling Reactions under Base- and Ligand-Free CuI-Zeolite Catalysis
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Various representative copper(I)-exchanged zeolites were investigated for their catalytic potential in Chan-Lam cross-coupling reactions. CuI-USY appeared as the best catalyst and proved to efficiently promote C-N cross-coupling processes under attractive, simple, and practical conditions, namely refluxing in methanol under air and without any base.
- Garnier, Tony,Sakly, Randa,Danel, Mathieu,Chassaing, Stefan,Pale, Patrick
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- Cu2O/Cs2CO3/DMF: An efficient catalytic system for N-arylation of imidazole with aryl halides under ligand-free conditions
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A ligand-free Cu-catalyzed protocol for the Ullmann-type N-arylation of N-containing heterocycles with aryl or heteroaryl iodides and bromides has been established. A broad range of functional groups is well tolerated on both of the cross-coupling partners, producing the desired products in good to excellent yields.
- Wang, Xiaochuang,Wang, Meiji,Xie, Jianwei
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- Ninhydrin: an efficient ligand for the Cu-catalyzed N-arylation of nitrogen-containing heterocycles with aryl halides
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Cu2O/ninhydrin was found to be an efficient catalyst system for the N-arylation of nitrogen-containing heterocycles with aryl and heteroaryl iodides, bromides and even unactivated chlorides to give the products in moderate to excellent yields.
- Huang, Yi-Zheng,Gao, Jin,Ma, Hong,Miao, Hong,Xu, Jie
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- An efficient diamine·copper complex-catalyzed coupling of arylboronic acids with imidazoles
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(Equation presented) A novel diamine·copper complex-catalyzed intermolecular coupling of arylboronic acids (1) with imidazoles (3) is described. In the presence of a catalytic amount of [Cu(OH)·TMEDA]2Cl2 (2), arylboronic acids (1) react smoothly with imidazoles (3) in dichloromethane at room temperature to give a variety of N-arylimidazoles (4) in good to excellent yields.
- Collman, James P.,Zhong, Min
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- A green, homogeneous and reusable surfactant/copper based ionic liquid for the N-arylation of indoles, pyrazoles and imidazoles
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An efficient surfactant/copper based ionic liquid promoter was examined as a reusable system for the N-arylation of indole, pyrazole and imidazole by a variety of aryl halides. The products were obtained in good to excellent yields by a convenient one-pot procedure. The reaction could be carried out in water under air and did not require the use of arylboronic acids as the active aryl source, palladium as the catalyst or a strong base.
- Heidarizadeh, Fariba,Majdi-Nasab, Afrooz
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- Simple copper salt-catalyzed N-arylation of nitrogen-containing heterocycles with aryl and heteroaryl halides
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(Chemical Equation Presented) Relatively mild and highly efficient CuI-catalyzed N-arylation procedures for nitrogen-containing heterocycles (e.g., imidazoles, benzimidazoles, pyrroles, pyrazoles, indoles, triazoles, etc.) with aryl and heteroaryl halides have been developed. The protocols can be performed easily and tolerate a number of functional groups, such as ester, nitrile, nitro, ketone, free hydroxyl, and free primary amine on the aryl halide.
- Zhu, Liangbo,Guo, Peng,Li, Gaocan,Lan, Jingbo,Xie, Rugang,You, Jingsong
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- Highly efficient copper-catalyzed N-arylation of nitrogen-containing heterocycles with aryl and heteroaryl halides
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(Chemical Equation Presented) New (S)-pyrrolidinylmethylimidazole ligands (4a-c) have been readily synthesized in a straightforward fashion from least expensive starting materials in short steps in high yields. Relatively mild and highly efficient Cul-catalyzed N-arylation procedures for imidazoles with aryl and heteroaryl bromides or chlorides have been developed in the presence of 4a and Cs2CO3. It is important to note that the protocol could tolerate functional groups such as ester, nitrile, nitro, ketone, free hydroxyl, and free primary amine on the aryl halide. The protocol could also be applicable to other π-electron-rich nitrogen heterocycles (pyrrole, pyrazole, indole, benzimidazole, and triazole), affording the N-arylazoles in good to excellent yields.
- Zhu, Liangbo,Cheng, Liang,Zhang, Yuxi,Xie, Rugang,You, Jingsong
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- A simple copper salt catalysed the coupling of imidazole with arylboronic acids in protic solvent
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In the presence of a catalytic amount of a simple copper salt, the coupling of imidazole with arylboronic acids was performed in methanol to give corresponding N-arylimidazoles in almost quantitative yields; this coupling reaction could also be performed in aqueous solutions to give N-arylimidazoles in excellent yields.
- Lan, Jing-Bo,Chen, Li,Yu, Xiao-Qi,You, Jing-Song,Xie, Ru-Gang
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- Correction to: Polyfunctional Imidazolium Aryloxide Betaine/Lewis Acid Catalysts as Tools for the Asymmetric Synthesis of Disfavored Diastereomers (Journal of the American Chemical Society (2019) 141 (12029-12043) DOI: 10.1021/jacs.9b04902)
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Page 12035 and Supporting Information pp S91-S94. It has come to our attention that the wrong initial concentration of 1a was erroneously used in two experiments of the "same excess" protocol.1 The experiments were thus repeated (0.055 rather than 0.06 mol/L of 1a was erroneously used before), and an excellent overlay of the "time-adjusted same excess" reaction profiles and the standard reaction profile, as previously presented, was found. This indicates that no significant catalyst deactivation takes place and that the active catalyst concentration remains constant during the catalytic reaction. The conclusions are thus not affected by the unintentional error. The corrected Figure 1 is shown below, and a corrected including Figures S1-S28 and Tables S1-S8 (corrected).(Figure Persented).Supporting Information file is available, in which pp S91?S94 have been replaced, in which the correct kinetic experiments are described, including raw data. We apologize for any inconvenience.
- Willig, Felix,Lang, Johannes,Hans, Andreas C.,Ringenberg, Mark R.,Pfeffer, Daniel,Frey, Wolfgang,Peters, René
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- Azole-Based Indoleamine 2,3-Dioxygenase 1 (IDO1) Inhibitors
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The heme enzyme indoleamine 2,3-dioxygenase 1 (IDO1) plays an essential role in immunity, neuronal function, and aging through catalysis of the rate-limiting step in the kynurenine pathway of tryptophan metabolism. Many IDO1 inhibitors with different chemotypes have been developed, mainly targeted for use in anti-cancer immunotherapy. Lead optimization of direct heme iron-binding inhibitors has proven difficult due to the remarkable selectivity and sensitivity of the heme-ligand interactions. Here, we present experimental data for a set of closely related small azole compounds with more than 4 orders of magnitude differences in their inhibitory activities, ranging from millimolar to nanomolar levels. We investigate and rationalize their activities based on structural data, molecular dynamics simulations, and density functional theory calculations. Our results not only expand the presently known four confirmed chemotypes of sub-micromolar heme binding IDO1 inhibitors by two additional scaffolds but also provide a model to predict the activities of novel scaffolds.
- R?hrig, Ute F.,Majjigapu, Somi Reddy,Reynaud, Aline,Pojer, Florence,Dilek, Nahzli,Reichenbach, Patrick,Ascencao, Kelly,Irving, Melita,Coukos, George,Vogel, Pierre,Michielin, Olivier,Zoete, Vincent
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p. 2205 - 2227
(2021/03/01)
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- Synthesis and Physical Properties of Tunable Aryl Alkyl Ionic Liquids (TAAILs)
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Tunable aryl alkyl ionic liquids (TAAILs) based on the imidazolium cation were first reported in 2009. Since then, a series of TAAILs with different properties due to the electron-donating or -withdrawing effect of the substituents at the aryl ring has be
- Lerch, Swantje,Strassner, Thomas
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supporting information
p. 15554 - 15557
(2021/10/06)
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- N -Arylation of (hetero)arylamines using aryl sulfamates and carbamates via C-O bond activation enabled by a reusable and durable nickel(0) catalyst
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An effective and general aryl amination protocol has been developed using a magnetically recoverable Ni(0) based nanocatalyst. This new stable catalyst was prepared on Fe3O4@SiO2 modified by EDTA and investigated by FT-IR, EDX, TEM, XRD, DLS, FE-SEM, XPS, NMR, TGA, VSM, ICP and elemental analysis techniques. The reaction proceeded via carbon-oxygen bond cleavage of (hetero)aryl carbamates and sulfamates under simple and mild conditions without the use of any external ligands. This method demonstrated functional group tolerance in the N-arylation of various nitrogen-containing compounds as well as aliphatic amines, anilines, pyrroles, pyrazoles, imidazoles, indoles, and indazoles with good to excellent yields. Furthermore, the catalyst could be easily recovered by using an external magnetic field and directly reused at least six times without notable reduction in its activity. This journal is
- Dindarloo Inaloo, Iman,Majnooni, Sahar,Eslahi, Hassan,Esmaeilpour, Mohsen
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p. 13266 - 13278
(2020/10/07)
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- Facile synthesis of hydrochar supported copper nanocatalyst for Ullmann C–N coupling reaction in water
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The exploration of inexpensive and stable heterogeneous catalysts and application of green solvents for Ullmann C–N coupling reaction remain challenging. We present a facile fabrication of copper nanoparticles on hydrochar as prepared from natural, inexpensive and renewable chitosan together with in-situ reduction of copper salt in a one-pot hydrothermal carbonization process. The copper nanoparticles were uniformly dispersed on hydrochar by choosing block copolymer F127 as surfactant. Moreover, maleic acid was introduced to improve the hydrophilicity of hydrochar. The most active copper nanocomposite catalyst, that is, Cu/HCS-MA-F127, exhibited excellent catalytic activity for Ullmann C–N coupling reaction in water. The nature of the Cu/HCS-MA-F127 was characterized by FTIR spectroscopy, TG, XRD, SEM and XPS. Moderate to excellent yields of aimed products were gained by using this catalytic strategy. Moreover, the Cu/HCS-MA-F127 catalyst can be reused by simple centrifugal recovery with a stable performance.
- Ge, Xin,Ge, Meng,Chen, Xinzhi,Qian, Chao,Liu, Xuemin,Zhou, Shaodong
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- HERBICIDAL COMPOUNDS
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The present invention relates to compounds of Formula (I) or an agronomically acceptable salt of said compounds wherein Q, R1, R2, n and m are as defined herein. The invention further relates to herbicidal compositions which comprise a compound of Formula (I) and to the use of compounds of Formula (I) for controlling weeds, in particular in crops of useful plants.
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Page/Page column 28
(2020/06/01)
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- L -(-) -Quebrachitol as a Ligand for Selective Copper(0)-Catalyzed N-Arylation of Nitrogen-Containing Heterocycles
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l-(-)-Quebrachitol (QCT) has been found as a ligand of copper powder for selective N-arylation of nitrogen-containing heterocycles with aryl halides. Furthermore, another potential catalytic system (copper powder/QCT/t-BuOK) was successfully adapted to unactivated aryl chlorides.
- Zhou, Qifan,Du, Fangyu,Chen, Yuanguang,Fu, Yang,Sun, Wenjiao,Wu, Ying,Chen, Guoliang
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p. 8160 - 8167
(2019/06/28)
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- A Newly Designed Carbohydrate-Derived Alkylamine Promotes Ullmann Type C-N Coupling Catalyzed by Copper in Water
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A green and biodegradable carbohydrate-derived alkylamine was designed and employed as ligand for Ullmann type C-N coupling catalyzed by copper in water. The coupling of aryl iodide and N-nucleophiles were examined and moderate to excellent yields were obtained. In addition, the in-water coupling strategy was expanded successfully to the reaction of indoles with 4-iodoanisole. By measuring the solubility, it is speculated that carbohydrate-derived alkylamine plays the role of chelating copper and promoting the dissolution of 4-iodoanisole in water. Remarkably, this methodology was environmentally friendly and economical because of the use of aqueous media in place of organic solvents.
- Zhou, Guoquan,Chen, Wen,Zhang, Shihui,Liu, Xuemin,Yang, Zehui,Ge, Xin,Fan, Hua-Jun
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supporting information
p. 193 - 198
(2019/01/14)
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- Polyfunctional Imidazolium Aryloxide Betaine/Lewis Acid Catalysts as Tools for the Asymmetric Synthesis of Disfavored Diastereomers
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Enzymes are Nature's polyfunctional catalysts tailor-made for specific biochemical synthetic transformations, which often proceed with almost perfect stereocontrol. From a synthetic point of view, artificial catalysts usually offer the advantage of much broader substrate scopes, but stereocontrol is often inferior to that possible with natural enzymes. A particularly difficult synthetic task in asymmetric catalysis is to overwrite a pronounced preference for the formation of an inherently favored diastereomer; this requires a high level of stereocontrol. In this Article, the development of a novel artificial polyfunctional catalyst type is described, in which an imidazolium-aryloxide betaine moiety cooperates with a Lewis acidic metal center (here Cu(II)) within a chiral catalyst framework. This strategy permits for the first time a general, highly enantioselective access to the otherwise rare diastereomer in the direct 1,4-addition of various 1,3-dicarbonyl substrates to β-substituted nitroolefins. The unique stereocontrol by the polyfunctional catalyst system is also demonstrated with the highly stereoselective formation of a third contiguous stereocenter making use of a diastereoselective nitronate protonation employing α,β-disubstituted nitroolefin substrates. Asymmetric 1,4-additions of β-ketoesters to α,β-disubstituted nitroolefins have never been reported before in literature. Combined mechanistic investigations including detailed spectroscopic and density functional theory (DFT) studies suggest that the aryloxide acts as a base to form a Cu(II)-bound enolate, whereas the nitroolefin is activated by H-bonds to the imidazolium unit and the phenolic OH generated during the proton transfer. Detailed kinetic analyses (RPKA, VTNA) suggest that (a) the catalyst is stable during the catalytic reaction, (b) not inhibited by product and (c) the rate-limiting step is most likely the C-C bond formation in agreement with the DFT calculations of the catalytic cycle. The robust catalyst is readily synthesized and recyclable and could also be applied to a cascade cyclization.
- Willig, Felix,Lang, Johannes,Hans, Andreas C.,Ringenberg, Mark R.,Pfeffer, Daniel,Frey, Wolfgang,Peters, René
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supporting information
p. 12029 - 12043
(2019/08/16)
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- Palladium-Catalyzed Methylation of Nitroarenes with Methanol
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A procedure for the synthesis of N-methyl-arylamines directly from nitroarenes using methanol as green methylating agent was developed. The key to success is the use of a specific catalyst system consisting of palladium acetate and the ligand 1-[2,6-bis(isopropyl)phenyl]-2-[tert-butyl(2-pyridinyl)phosphino]-1H-Imidazole (L1). The generality of this protocol is demonstrated in the synthesis of more than 20 N-methyl-arylamines under comparably mild conditions. Combining this novel methodology with subsequent coupling processes using the same catalyst allows for efficient diversification of aromatic nitro compounds to a broad variety of amines including drug molecules.
- Wang, Lin,Neumann, Helfried,Beller, Matthias
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supporting information
p. 5417 - 5421
(2019/04/04)
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- Fragment-Based Discovery of a Qualified Hit Targeting the Latency-Associated Nuclear Antigen of the Oncogenic Kaposi's Sarcoma-Associated Herpesvirus/Human Herpesvirus 8
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The latency-associated nuclear antigen (LANA) is required for latent replication and persistence of Kaposi's sarcoma-associated herpesvirus/human herpesvirus 8. It acts via replicating and tethering the virus episome to the host chromatin and exerts other functions. We conceived a new approach for the discovery of antiviral drugs to inhibit the interaction between LANA and the viral genome. We applied a biophysical screening cascade and identified the first LANA binders from small, structurally diverse compound libraries. Starting from a fragment-sized scaffold, we generated optimized hits via fragment growing using a dedicated fluorescence-polarization-based assay as the structure-activity-relationship driver. We improved compound potency to the double-digit micromolar range. Importantly, we qualified the resulting hit through orthogonal methods employing EMSA, STD-NMR, and MST methodologies. This optimized hit provides an ideal starting point for subsequent hit-to-lead campaigns providing evident target-binding, suitable ligand efficiencies, and favorable physicochemical properties.
- Kirsch, Philine,Jakob, Valentin,Oberhausen, Kevin,Stein, Saskia C.,Cucarro, Ivano,Schulz, Thomas F.,Empting, Martin
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-
- Fragment-Based Discovery of a Qualified Hit Targeting the Latency-Associated Nuclear Antigen of the Oncogenic Kaposi's Sarcoma-Associated Herpesvirus/Human Herpesvirus 8
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The latency-associated nuclear antigen (LANA) is required for latent replication and persistence of Kaposi's sarcoma-associated herpesvirus/human herpesvirus 8. It acts via replicating and tethering the virus episome to the host chromatin and exerts other functions. We conceived a new approach for the discovery of antiviral drugs to inhibit the interaction between LANA and the viral genome. We applied a biophysical screening cascade and identified the first LANA binders from small, structurally diverse compound libraries. Starting from a fragment-sized scaffold, we generated optimized hits via fragment growing using a dedicated fluorescence-polarization-based assay as the structure-activity-relationship driver. We improved compound potency to the double-digit micromolar range. Importantly, we qualified the resulting hit through orthogonal methods employing EMSA, STD-NMR, and MST methodologies. This optimized hit provides an ideal starting point for subsequent hit-to-lead campaigns providing evident target-binding, suitable ligand efficiencies, and favorable physicochemical properties.
- Kirsch, Philine,Jakob, Valentin,Oberhausen, Kevin,Stein, Saskia C.,Cucarro, Ivano,Schulz, Thomas F.,Empting, Martin
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p. 3924 - 3939
(2019/05/06)
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- Optimization of diarylpentadienones as chemotherapeutics for prostate cancer
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Our earlier studies indicate that (1E,4E)-1,5-bis(1-alkyl-1H-imidazol-2-yl)penta-1,4-diene-3-ones and (1E,4E)-1,5-bis(1-alkyl-1H-benzo[d]imidazol-2-yl)penta-1,4-diene-3-ones exhibit up to 121-fold greater antiproliferative potency than curcumin in human p
- Patanapongpibul, Manee,Zhang, Changde,Chen, Guanglin,Guo, Shanchun,Zhang, Qiang,Zheng, Shilong,Wang, Guangdi,Chen, Qiao-Hong
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p. 4751 - 4760
(2018/08/21)
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- Enhanced Catalytic Activity of Oxygen-Tethered IrIII NHC Complexes in Aqueous Transfer Hydrogenative Reductive Amination Reactions: Experimental Kinetic and Mechanistic Study
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The synthesis and characterization of seven new IrIII complexes containing o-phenoxide or o-naphthoxide chelated N-heterocyclic carbene ligands is reported herein. The crystal structures of six of the complexes have been determined. These complexes efficiently catalyze the transfer hydrogenative reductive amination (RA) of carbonyls and amines in water. Amongst the complexes tested, the introduction of o-naphthoxide on a nitrogen atom of imidazole based NHC ligand greatly increased the catalytic activity. The catalytic system has a broad substrate scope, which allows the synthesis of a variety of amines in excellent yields and with high turnover numbers up to 490 (for ketones) and 14800 (for aldehydes). The mechanism of aqueous RA reaction with an o-aryloxide chelated NHC-IrIII catalyst has been investigated by NMR spectroscopy and kinetic measurements. These studies suggest that the transfer hydrogenation (TH) is turnover-limited by the hydride formation step. As a result of the 1H NMR studies, the higher catalytic activity of o-naphthoxide chelated catalyst (3 g) over o-phenoxide chelated one (3 b) can be attributed partly due to the faster formation of an iridium hydride, the key intermediate in the RA reactions.
- ?zbozkurt, ?brahim Kayahan,Gülcemal, Derya,Günnaz, Salih,G?k?e, Ayta? Gürhan,?etinkaya, Bekir,Gülcemal, Süleyman
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p. 3593 - 3604
(2018/08/03)
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- Phenoxide chelated Ir(iii) N-heterocyclic carbene complexes: Synthesis, characterization, and evaluation of their in vitro anticancer activity
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Twelve novel half-sandwich IrIII-NHC complexes [(η5-Cpx)Ir(C^O)Cl] were synthesized and characterized. These complexes showed higher cytotoxic activity toward A549 cells and HeLa cells than cisplatin. An increase in the nu
- Zhang, Yujiao,Zhang, Shumiao,Tian, Zhenzhen,Li, Juanjuan,Xu, Zhishan,Li, Shanshan,Liu, Zhe
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supporting information
p. 13781 - 13787
(2018/10/20)
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- Chan-Lam cross-coupling reaction based on the Cu2S/TMEDA system
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A catalyst based on the readily available Cu2S/TMEDA system using a stable copper(I) source was developed for the Chan-Lam cross-coupling reaction. The capability of the catalyst was demonstrated with 1H-benzo[d]imidazol-2(3H)-one, 1H-benzo[d]imidazole, and 1H-imidazole together with electron-deficient, electron-rich, and sterically demanding boronic acids at room temperature in the presence of atmospheric oxygen to give the cross-coupling products in moderate to excellent yields. In addition, the coupling reaction of 1H-benzo[d]imidazole with several pinacol or neopentylglycol boronates indicated further potential of the catalyst. The reaction conditions tolerate the hydroxyl and bromo functional groups. The catalytic system also enables to synthesize the mono-N-substituted anilines from primary aliphatic amines. However, the two model compounds for the secondary and aromatic amines, piperidine and aniline, do not react. Two sterically demanding products with the restricted C–N bond rotation, synthesized by the N-arylation of 1H-benzo[d]imidazol-2(3H)-one with o-tolylboronic acid, enabled to confirm the atropisomers prepared by the Chan-Lam cross-coupling reaction. Furthermore, an example of one-pot Chan-Lam and Suzuki-Miyaura reaction has been reported.
- Janíková, Kate?ina,Jedinák, Luká?,Volná, Tereza,Canka?, Petr
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p. 606 - 617
(2018/01/01)
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- Carbothioamide as Highly Efficient Ligand for Copper-catalyzed Room Temperature Chan–Lam Cross-Coupling Reaction
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The catalytic activity of three N,S-donor ligands, viz L1 [2-(4-methoxybenzylidene)-N-phenylhydrazinecarbothioamide], L2 [2,2′-(1,2-diphenylethane-1,2-diylidene)bis(hydrazinecarbothioamide)] and L3 [2-(4-methoxybenzylidene)hydrazinecarbothioamide] has been reported for N-arylation of imidazoles with arylboronic acids in ethanol at room temperature. The method was found to be applicable in N-arylation for a wide range of electronically diverse arylboronic acids with imidazoles having modest to excellent isolated yields. The in situ generated copper(II) complex of the ligand namely, 2-(4-methoxybenzylidene)-N-phenylhydrazinecarbothioamide (L1) was found to be highly efficient homogeneous catalyst for N-arylation reaction.
- Baruah, Jayantajit,Gogoi, Kongkona,Dewan, Anindita,Borah, Geetika,Bora, Utpal
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p. 1203 - 1208
(2017/10/25)
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- Site-selective arene C-H amination via photoredox catalysis
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Over the past several decades, organometallic cross-coupling chemistry has developed into one of the most reliable approaches to assemble complex aromatic compounds from preoxidized starting materials. More recently, transition metal-catalyzed carbon-hydrogen activation has circumvented the need for preoxidized starting materials, but this approach is limited by a lack of practical amination protocols. Here, we present a blueprint for aromatic carbon-hydrogen functionalization via photoredox catalysis and describe the utility of this strategy for arene amination. An organic photoredox-based catalyst system, consisting of an acridinium photooxidant and a nitroxyl radical, promotes site-selective amination of a variety of simple and complex aromatics with heteroaromatic azoles of interest in pharmaceutical research. We also describe the atom-economical use of ammonia to form anilines, without the need for prefunctionalization of the aromatic component.
- Romero, Nathan A.,Margrey, Kaila A.,Tay, Nicholas E.,Nicewicz, David A.
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p. 1326 - 1330
(2015/10/12)
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- N-(1-Oxy-2-picolyl)oxalamic acids as a new type of O,O-ligands for the Cu-catalyzed N-arylation of azoles with aryl halides in water or organic solvent
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N-(1-Oxy-pyridin-2-ylmethyl)oxalamic acids (L3-L5) were identified as novel efficient ligands for copper-catalyzed C-N cross-coupling of azoles and aryl halides in water. The N-arylation of imidazoles, indoles and pyrazoles proceeded with moderate to excellent yields and complete selectivity over aromatic amines and phenols. Moreover, L5, which is also efficient in organic solvent with low catalyst loading, can be used to promote the N-arylation reactions with water-sensitive materials. The catalytic mechanism was proposed based on the results of several verification experiments which indicated that the ligands as new-type chelators may coordinate to Cu(i) with two oxygen atoms of N-oxide and amide in the coupling process. This journal is
- Wang, Yongbin,Zhang, Yu,Yang, Beibei,Zhang, Ao,Yao, Qizheng
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p. 4101 - 4114
(2015/03/30)
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- Air-stable palladium(0) phosphine sulfide catalysts for Ullmann-type C-N and C-O coupling reactions
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This paper describes an efficient procedure for palladium(0)-catalyzed N-arylation and O-arylation of aryl halides by Ullmann-type cross coupling reaction under mild reaction conditions in a short reaction time. Two phosphine sulphide ligands and their corresponding Pd(0) complexes namely [Pd(p2S2)(dba)] and [Pd(pp3S4)(dba)], were synthesized, where p2S2 is 1,2-bis(diphenylphosphino)ethane disulfide, pp3S4 is tris[2-(diphenylphosphino)ethyl]phosphine tetrasulfide and dba is dibenzylideneacetone. Optimal reaction conditions were determined for the arylation reactions using iodobenzene and benzimidazole by varying temperature, solvent, base and catalyst loading. The cross coupling reactions were carried out taking iodobenzenes/bromobenzenes and a wide variety of substituted aryl amines/phenols/alcohols with different steric and electronic properties to afford the desired N-aryl amines/diaryl ethers/alkyl aryl ethers in good to excellent yield (70-94%).
- Majumder, Arpi,Gupta, Ragini,Mandal, Mrinmay,Babu, Madhu,Chakraborty, Debashis
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- Direct C-N coupling of imidazoles with aromatic and benzylic compounds via electrooxidative C-H functionalization
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A method for the C-N coupling of imidazoles based on electrooxidative C-H functionalization of aromatic and benzylic compounds has been developed. The key to the success is the formation of protected imidazolium ions as initial products, avoiding overoxidation. Deprotection under nonoxidative conditions affords N-substituted imidazoles. Various functional groups are compatible with the present transformation. To demonstrate the power of the method, a P450 17 inhibiter and an antifungal agent having N-substituted imidazole structures were synthesized.
- Morofuji, Tatsuya,Shimizu, Akihiro,Yoshida, Jun-Ichi
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supporting information
p. 4496 - 4499
(2014/04/17)
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- 4,5-DIHYDROISOXAZOLE DERIVATIVES AS NAMPT INHIBITORS
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The present invention provides substituted 4,5-dihydroisoxazole derivatives of formula (I), which may be therapeutically useful, more particularly NAMPT inhibitors and in which R1 R2, Y, X, "Het" and "p" have the meanings given in the specification, and pharmaceutically acceptable salts thereof that are useful in the treatment and prevention of diseases or disorder caused by an elevated level of nicotinamide phosphoribosyltransferase (NAMPT) in a mammal. The present invention also provides preparation of the compounds and pharmaceutical formulations comprising at least one of the substituted 4,5-dihydroisoxazole derivatives of formula (I) or a pharmaceutically acceptable salts or stereoisomers or N-oxide thereof.
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Page/Page column 177; 178
(2014/08/06)
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- PYRAZOLO[3,4-D]PYRIMIDIN-4(5H)-ONE DERIVATIVES AS PDE9 INHIBITORS
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A compound of the general formula (I) wherein R1 is selected from the group consisting of phenyl unsubstituted or substituted with 1 to 3 substituents selected from F, Cl, Br, I, CN, -O-C1-C3-alkyl, fluorinated -O-C1-C3-alkyl, -(CH2)mOH and 5-membered heterocyclic group with 1 or 2 heteroatoms selected from N, O and S; and 6- or 10-membered heteroaryl with 1 to 3 heteroatoms selected from O, N and S; R2 and R3 independently of each other represent H atom or straight or branched C1-C3 alkyl; R4 is selected from the group consisting of 4- to 6- membered cycloalkyl, wherein one of carbon atoms can be replaced by O atom, and which is unsubstituted or substituted with one or two halogen atoms,and straight or branched C1-C4 alkyl; Q represents a bond or C1-C3-alkylene, which can be optionally substituted by one to three C1-C3-alkyls; X is selected from the group consisting of O, NR5, and S(O)p; R5 represents H atom or C1-C3alkyl; m is 1, 2 or 3; p is 0, 1 or 2; and salts thereof, for use as a medicament, in particular for treating cognitive function disorders and neurodegenerative diseases.
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Page/Page column 31
(2014/02/16)
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- 8-Hydroxyquinoline functionalized peg-1000 bridged Dicationic ionic liquid as a novel Ligand for copper-catalyzed n-Arylation of Imidazoles
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A novel 8-hydroxyquinoline functionalized PEG-1000 bridged dicationic ionic liquid ([HQ-PEG1000- DIL][BF4]) was synthesized and characterized. It was applied as an efficiently recyclable ligand for copper- catalyzed N-arylation of nitrogen-containing heterocycles with aryl halides. The catalytic system could be easily recovered and reused for at least five runs without obvious loss of catalytic activity.
- Wang, Ying-Lei,Luo, Jun,Liu, Zu-Liang
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p. 1007 - 1013
(2013/10/22)
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- Palladium(II)-catalyzed Heck reaction of aryl halides and arylboronic acids with olefins under mild conditions
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A series of general and selective Pd(II)-catalyzed Heck reactions were investigated under mild reaction conditions. The first protocol has been developed employing an imidazole-based secondary phosphine oxide (SPO) ligated palladium complex (6) as a precatalyst. The catalytic coupling of aryl halides and olefins led to the formation of the corresponding coupled products in excellent yields. A variety of substrates, both electron-rich and electron-poor olefins, were converted smoothly to the targeted products in high yields. Compared with the existing approaches employing SPO-Pd complexes in a Heck reaction, the current strategy features mild reaction conditions and broad substrate scope. Furthermore, we described the coupling of arylboronic acids with olefins, which were catalyzed by Pd(OAc)2 and employed N-bromosuccinimide as an additive under ambient conditions. The resulted biaryls have been obtained in moderate to good yields.
- Shaikh, Tanveer Mahamadali,Hong, Fung-E
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supporting information
p. 1578 - 1588
(2013/10/22)
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- Palladium-catalyzed β-arylation of silyl ketene acetals and application to the synthesis of benzo-fused δ-lactones
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Silyl ketene acetals are shown to be competent nucleophiles in Pd-catalyzed migrative C(sp3)-H arylations. Compared to the parent ester lithium enolates, they possess decreased reactivity but enhanced chemoselectivity. This behavior was exploited through the synthesis of valuable benzo-fused δ-lactones such as 1-isochromanones and dihydrocoumarins.
- Aspin, Sam,Lopez-Suarez, Laura,Larini, Paolo,Goutierre, Anne-Sophie,Jazzar, Rodolphe,Baudoin, Olivier
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supporting information
p. 5056 - 5059
(2013/10/22)
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- Benzotriazol-1-ylmethanol: An excellent bidentate ligand for the copper/palladium-catalyzed C-N and C-C coupling reaction
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An efficient benzotriazole based N,O bidentate ligands for the Cu-catalyzed N-arylation of π-excessive nitrogen heterocycles is described. This ligand accomplishes C-N coupling of Nheterocycles and C-C coupling of boronic acids with a variety of hindered, functionalized aryl/heteroaryl halides under mild reaction conditions in good to excellent yields. Using his ligand C-N and C-C (Suzuki) couplings with bromoarenes could be conducted with less catalyst loading. A wide array of deactivated and hindered aryl halides react cleanly to afford the functionalized biaryl derivatives in high yields. ARKAT-USA, Inc.
- Jha, Rajeev R.,Singh, Jaspal,Tiwari, Rakesh K.,Verma, Akhilesh K.
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p. 228 - 248
(2013/02/23)
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