- Anxiolytic- and antidepressant-like effects of new phenylpiperazine derivative LQFM005 and its hydroxylated metabolite in mice
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The current treatments available for anxiety and depression are only palliative. Full remission has remained elusive, characterizing unmet medical needs. In the scope of an academic drug discovery program, we describe here the design, synthesis, in vitro metabolism prediction and pharmacological characterization of a new piperazine compound, 1-(4-methoxyphenyl)?4-((1-phenyl-1H-pyrazol-4-yl)methyl)piperazine (LQFM005), and of its main putative metabolite, 4-(4-((4-(4-methoxyphenyl)piperazin-1-yl)methyl)? 1H-pyrazol-1-yl)phenol (LQFM235). The production of the metabolite was initially performed by in vitro biotransformation of LQFM005 using Aspergillus candidus and then by chemical synthesis. Oral administration of either 12 or 24 μmol/kg LQFM005 to mice did not affect spontaneous locomotor activity but increased the time spent in the center of the open field. Both LQFM005 and LQFM235 (24 μmol/kg) increased the time spent by the mice in the open arms of the elevated plus maze (EPM), a good indication of anxiolytic-like effect, and decreased the immobility time in the forced swimming test (FST), suggesting an antidepressant-like effect. The previous administration of WAY-100635 (a 5-HT1A antagonist) abolished the effects of LQFM005 in both EPM and FST. Binding experiments showed that LQFM005 and its metabolite bind to the 5-HT1A receptor with a moderate affinity (Ki around 5–9 μM). The two compounds are relatively safe, as indicated by cytotoxic assessment using the 3T3 fibroblast cell line and estimated LD50 around 600 mg/kg. In conclusion, oral administration of the newly synthesized phenylpiperazines produced anxiolytic- and antidepressant-like effects in behavioral tests, putatively in part through the activation of 5-HT1A receptors.
- Moreira, Lorrane Kelle da Silva,Silva, Rafaela Ribeiro,da Silva, Dayane Moreira,Mendes, Mirella Andrade Silva,de Brito, Adriane Ferreira,de Carvalho, Flávio Souza,Sanz, Germán,Rodrigues, Marcella Ferreira,da Silva, Artur Christian Garcia,Thomaz, Douglas Vieira,de Oliveira, Valéria,Vaz, Boniek Gontijo,Li?o, Luciano Morais,Valadares, Marize Campos,Gil, Eric de Souza,Costa, Elson Alves,No?l, Fran?ois,Menegatti, Ricardo
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- Copper pyrithione (CuPT)-catalyzed/mediated amination and thioarylation of (hetero)aryl halides: A competition
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A facile method for the synthesis of N-arylheterocycles and di(hetero)aryl sulfides under mild condition is described. In these transformations, copper pyrithione (CuPT) was used as the copper catalyst for C─N coupling, while served as catalyst and coupled partner for C─S coupling with high yields and broad substrate tolerance. The S-arylation process was also utilized for the construction of valuable bioactive 2-sulfonylpyridine 1-oxide derivatives.
- Cao, Ningtao,Song, Bao,Xie, Jianwei,Zhang, Jie
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- A post-synthetically modified metal-organic framework for copper catalyzed denitrative C-N coupling of nitroarenes under heterogeneous conditions
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Here we report, for the first time, the Ullmann C-N coupling reaction of nitroarenes which is achieved by using a copper containing metal-organic framework (MOF) catalyst under heterogenous conditions. The ready availability of nitroarenes and their low cost have made them ideal replacements for haloarenes as electrophilic coupling partners. Notably, the reaction protocol suppresses the by-product formation in the catalytic reaction. The catalyst has been designed and synthesized by two step post-synthesis functionalization of a MOF,viz.dabco MOF-1 with a -NH2functional group (DMOF-NH2). In the post-synthetic treatment, salicylaldehyde has been used for organic modification first and then copper(ii) was successfully incorporated onto the inner surface of the porous material. The hybrid porous solid thus obtained has been employed in the catalytic C-N coupling reaction of nitroarenes with a wide variety of amines under heterogeneous conditions, which displayed very high turnover frequencies (TOF) in catalytic reactions attesting its efficacy towards theN-arylation reaction.
- Maity, Tanmoy,Ghosh, Pameli,Das, Soma,Saha, Debraj,Koner, Subratanath
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p. 5568 - 5575
(2021/04/06)
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- Dehydrogenative Azolation of Arenes in a Microflow Electrochemical Reactor
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The electrochemical synthesis of aryl azoles was performed for the first time in a microflow reactor. The reaction relies on the anodic oxidation of the arene partners making these substrates susceptible for C-H functionalization with azoles, thus requiring no homogeneous transition-metal-based catalysts. The synthetic protocol benefits from the implementation of a microflow setup, leading to shorter residence times (10 min), compared to previously reported batch systems. Various azolated compounds (22 examples) are obtained in good to excellent yields.
- Buglioni, Laura,Besla?, Marko,No?l, Timothy
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supporting information
p. 16195 - 16203
(2021/09/13)
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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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- The Hofmann reaction involving annulation of: O -(pyridin-2-yl)aryl amides selectively and rapidly leads to potential photocatalytically active 6 H -pyrido[1,2- c] quinazolin-6-one derivatives
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A highly efficient PIFA-mediated Hofmann reaction of o-(pyridin-2-yl)aryl amides has been developed to selectively and rapidly construct various potential photocatalytically active 6H-pyrido[1,2-c]quinazolin-6-one derivatives. The use of a nontoxic and ec
- Gao, Wenjing,Liu, Tongxin,Wan, Yameng,Wu, Hao,Zhang, Guisheng,Zhang, Zhiguo
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supporting information
p. 7955 - 7961
(2020/11/30)
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- Metal-free Semiconductor Photocatalysis for sp2 C?H Functionalization with Molecular Oxygen
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Designing metal-free catalysts for solar energy conversion is a long-standing challenge in semiconductor photoredox catalysis (SPC). With visible-light-responsive hexagonal boron carbon nitride (h-BCN) as a non-metal photocatalyst, this system affords C?H/N?H coupling products with broad substitution tolerance and high efficiency with molecular oxygen as the terminal oxidant. The catalyst exhibits remarkable performance for the selective C?H functionalization of electron-rich arenes to C?N products (yields up to 95 %) and good stability (6 recycles). Both nitrogen heteroarenes and amine salts are competent coupling nucleophiles. Mechanically, the reactive oxygen species are superoxide anion radical (O2?.) and H2O2, which are proved by electron spin resonance (ESR) data, KI-starch, and control experiments. In addition, kinetic isotope effect (KIE) experiments indicate that C?H bond cleavage is not involved in the rate limiting step. This semiconductor-based photoredox system allows for C?H amination free of any metals, ligands, strong oxidants, and additives. It provides a complementary avenue to C?H functionalizations and enables synthetic applications efficiently in a sustainable manner.
- Zheng, Meifang,Ghosh, Indrajit,K?nig, Burkhard,Wang, Xinchen
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p. 703 - 706
(2019/01/04)
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- Regioselective Ortho Amination of an Aromatic C-H Bond by Trifluoroacetic Acid via Electrochemistry
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A trifluoroacetic acid-facilitated ortho amination of alkoxyl arene has been established via anodic oxidation in an undivided cell. In the absence of any additional metal or oxidant reagents, a series of aromatic and heteroaromatic amine derivatives have
- Wang, Jing-Hao,Lei, Tao,Nan, Xiao-Lei,Wu, Hao-Lin,Li, Xu-Bing,Chen, Bin,Tung, Chen-Ho,Wu, Li-Zhu
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supporting information
p. 5581 - 5585
(2019/08/01)
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- Photocatalytic Oxidative Iodination of Electron-Rich Arenes
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A visible-light-mediated oxidative iodination of electron-rich arenes has been developed. 2.5 mol% of unsubstituted anthraquinone as photocatalyst were used in combination with elementary iodine, trifluoroacetic acid and oxygen as the terminal oxidant. The iodination proceeds upon irradiation in non- or weakly-electron donating solvents (DCM, DCE and benzene) wherein a spectral window in strongly coloured iodine solutions can be observed at around 400 nm. The method provides good to excellent yields (up to 98%) and shows excellent regioselectivity and good functional group tolerance (triple bonds, ketone, ester, amide). Moreover, the photo-iodination was also upscaled to a 5 mmol scale (1.1 g). Mechanistic investigations by intermediate trapping and competition experiments indicate a photocatalytic arene oxidation and the subsequent reaction with iodine as a likely mechanistic pathway. (Figure presented.).
- Narobe, Rok,Düsel, Simon J. S.,Iskra, Jernej,K?nig, Burkhard
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supporting information
p. 3998 - 4004
(2019/07/17)
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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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- Design, synthesis, and evaluation of indeno[2,1-c]pyrazolones for use as inhibitors against hypoxia-inducible factor (HIF)-1 transcriptional activity
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HIF-1 is regarded as a promising target for the drugs used in cancer chemotherapy, and creating readily accessible templates for the development of synthetic drug candidates that could inhibit HIF-1 transcriptional activity is an important pursuit. In this study, indeno[2,1-c]pyrazolones were designed as readily available synthetic inhibitors of HIF-1 transcriptional activity. Nine compounds were synthesized in 4–5 steps from commercially available starting materials. In evaluations of the ability to inhibit the hypoxia-induced transcriptional activity of HIF-1, compound 3c showed a higher level compared with that of known inhibitor, YC-1. The compound 3c suppressed HIF-1α protein accumulation without affecting the levels of HIF-1α mRNA.
- Fuse, Shinichiro,Kadonosono, Tetsuya,Kizaka-Kondoh, Shinae,Kuchimaru, Takahiro,Nakamura, Hiroyuki,Sato, Shinichi,Suzuki, Kensuke,Ueda, Hiroki
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supporting information
(2019/11/26)
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- C?N Cross-Coupling Reactions Under Mild Conditions Using Singlet Di-Radical Nickel(II)-Complexes as Catalyst: N-Arylation and Quinazoline Synthesis
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Herein we report a cost-effective synthetic approach for C?N cross-coupling reactions of a broad array of nitrogen nucleophiles and aryl halides under mild conditions. These reactions are catalyzed by an inexpensive, air-stable, earth-abundant and easy-to-prepare singlet di-radical nickel(II)-catalyst containing two antiferromagnetically coupled single-electron oxidized diiminosemiquinonato type ligands. This protocol provides an alternative method for C?N cross-coupling reactions avoiding nickel(0)/nickel(II) or nickel(I)/nickel(III) redox processes via cooperative participation of metal and ligand-centered redox events. Besides a wide range of N-arylation reactions, by judicious choice of aryl halides and nitrogen nucleophiles the synthesis of a variety of polysubstituted quinazolines has been achieved in moderate to good yields under relatively mild reaction conditions. Our catalyst has been found to be almost equally effective in quinazoline synthesis via C?N cross-coupling of (i) 2-bromobenzylamine with benzamide, and (ii) 2-bromobenzylbromide with amidine. Control experiments and DFT studies were performed to improve the understanding of the cooperative participation of ligand and metal (nickel)-centered redox events during oxidative addition/reductive elimination processes of the catalytic cycle and to shed light on the plausible mechanistic pathway of the C?N cross-coupling reactions. (Figure presented.).
- Sikari, Rina,Sinha, Suman,Chakraborty, Gargi,Das, Siuli,van Leest, Nicolaas Petrus,Paul, Nanda D.
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supporting information
p. 4342 - 4353
(2019/08/21)
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- SSAO INHIBITORS AND USES THEREOF
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Described herein are compounds that are semicarbazide-sensitive amine oxidase (SSAO) inhibitors, methods of making such compounds, pharmaceutical compositions and medicaments comprising such compounds, and methods of using such compounds in treating or preventing a liver disease or condition.
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Paragraph 00378
(2020/01/08)
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- Iron-Catalyzed/Mediated C-N Bond Formation: Competition between Substrate Amination and Ligand Amination
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Iron catalyzed carbon-nitrogen bond formation reactions of a wide variety of nucleophiles and aryl halides using well-defined iron-complexes featuring redox noninnocent 2-(arylazo)-1,10-phenanthroline (L1) ligands are reported. Besides substrate centered C-N coupling, C-N bond formation reactions were also observed at the ortho- and para-positions of the phenyl ring of the coordinated azo-aromatic scaffolds affording new tetradentate ligands, 2-N-aryl-(2-arylazo)-1,10-phenanthroline (L2), and tridentate ligands, 4-N-aryl-(2-arylazo)-1,10-phenanthroline (L3), respectively. Control experiments and mechanistic studies reveal that the complex [FeL1Cl2] (1) undergoes in situ reduction during the catalytic reaction to produce the monoanionic complex [1]-, which then acts as the active catalyst. The metal (iron) and the coordinated ligand were found to work in a cooperative manner during the transfer processes involved in the fundamental steps of the catalytic cycle. Detailed experimental and theoretical (DFT) studies were performed to get insight into the competitive substrate versus ligand centered amination reactions.
- Sinha, Suman,Sikari, Rina,Sinha, Vivek,Jash, Upasona,Das, Siuli,Brand?o, Paula,Demeshko, Serhiy,Meyer, Franc,De Bruin, Bas,Paul, Nanda D.
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p. 1935 - 1948
(2019/01/25)
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- Ruthenium-Catalyzed ortho- And meta-H/D Exchange of Arenes
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Ruthenium-catalyzed aromatic H/D exchange in [D4]acetic acid has been developed. By using N-heteroarenes as directing groups, both ortho and meta positions are selectively deuterated with high levels of D incorporation. Moreover, this strategy provides an alternative way to achieve meta-C-H activation.
- Zhao, Liang-Liang,Liu, Wei,Zhang, Zengyu,Zhao, Hongyan,Wang, Qi,Yan, Xiaoyu
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supporting information
p. 10023 - 10027
(2019/12/24)
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- Oxalic amide ligands, and uses thereof in copper-catalyzed coupling reaction of aryl halides
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The present invention provides oxalic amide ligands and uses thereof in copper-catalyzed coupling reaction of aryl halides. Specifically, the present invention provides a use of a compound represented by formula I, wherein definitions of each group are described in the specification. The compound represented by formula I can be used as a ligand in copper-catalyzed coupling reaction of aryl halides for the formation of C—N, C—O and C—S bonds.
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Page/Page column 116
(2020/01/09)
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- Copper(I)-USY as a Ligand-Free and Recyclable Catalyst for Ullmann-Type O-, N-, S-, and C-Arylation Reactions: Scope and Application to Total Synthesis
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The copper(I)-doped zeolite CuI-USY proved to be a versatile, efficient, and recyclable catalyst for various Ullmann-type coupling reactions. Easy to prepare and cheap, this catalytic material enables the arylation and heteroarylation of diverse O-, N-, S-, and C-nucleophiles under ligand-free conditions while exhibiting large functional group compatibility. The facility of this catalyst to promote C-O bond formation was further demonstrated with the total synthesis of 3-methylobovatol, a naturally occurring diaryl ether of biological relevance. From a mechanistic viewpoint, two competitive pathways depending on the nature of the nucleophile and consistent with the obtained results have been proposed.
- Garnier, Tony,Danel, Mathieu,Magné, Valentin,Pujol, Anthony,Bénéteau, Valérie,Pale, Patrick,Chassaing, Stefan
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p. 6408 - 6422
(2018/05/31)
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- Ruthenium-Catalyzed meta-Selective C?H Mono- and Difluoromethylation of Arenes through ortho-Metalation Strategy
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The first example for the ruthenium-catalyzed ligand-directed meta-selective C?H mono- and difluoromethylation is developed, affording a variety of new meta-mono- and difluoromethylated 2-phenylpyridines, 2-phenylpyrimidines, and 1-phenylpyrazoles in moderate-to-good yields. This new transformation exhibits broad substrate scope, good functional group tolerance, and high efficiency, and offers a practical approach to synthesize mono- and difluoromethylated arenes. Mechanistic studies indicate that a reaction pathway involving palladium-initiated radical species is involved in the catalytic cycle. The new dual catalytic system consisting of compatible ruthenium(II) and palladium(0) complexes enables the key processes of C?H activation and mono-/difluoromethyl-radical formation to occur and achieves the meta-selective functionalization efficiently. In addition, the present protocol can also be extended to non-fluoromethylation.
- Li, Zhong-Yuan,Li, Liang,Li, Qi-Li,Jing, Kun,Xu, Hui,Wang, Guan-Wu
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supporting information
p. 3285 - 3290
(2017/03/16)
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- Intermolecular Aryl C?H Amination through Sequential Iron and Copper Catalysis
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A mild, efficient and regioselective method for para-amination of activated arenes has been developed through a combination of iron and copper catalysis. A diverse range of products were obtained from an operationally simple one-pot, two-step procedure involving bromination of the aryl substrate with the powerful Lewis acid iron(III) triflimide, followed by a copper(I)-catalysed N-arylation reaction. This two-step dehydrogenative process for the regioselective coupling of aromatic C?H bonds with non-activated amines was applicable to anisole-, phenol-, aniline- and acetanilide-type aryl compounds. Importantly, the arene substrates were used as the limiting reagent and required no protecting-group manipulations during the transformation.
- Mostafa, Mohamed A. B.,Calder, Ewen D. D.,Racys, Daugirdas T.,Sutherland, Andrew
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p. 1044 - 1047
(2017/02/05)
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- Teaching Old Compounds New Tricks: DDQ-Photocatalyzed C?H Amination of Arenes with Carbamates, Urea, and N-Heterocycles
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The C?H amination of benzene derivatives was achieved using DDQ as photocatalyst and BocNH2 as the amine source under aerobic conditions and visible light irradiation. Electron-deficient and electron-rich benzenes react as substrates with moderate to good product yields. The amine scope of the reaction comprises Boc-amine, carbamates, pyrazoles, sulfonimides and urea. Preliminary mechanistic investigations indicate arene oxidation by the triplet of DDQ to radical cations with different electrophilicity and a charge transfer complex between the amine and DDQ as intermediate of the reaction.
- Das, Somnath,Natarajan, Palani,K?nig, Burkhard
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supporting information
p. 18161 - 18165
(2017/12/28)
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- A pyrazolyl pyrimidine compound and use thereof
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The present invention discloses a pyrazolyl pyrilamine compound, the compound has a structure as shown in formula (I), and the substituent groups in the (I) are as defined in the specification. The pyrazolyl pyrilamine compound has good control effects on downy mildew of cucumber, puccinia polysra, wheat powdery mildew and other diseases, and is especially better in the control effect on the downy mildew of cucumber.
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-
Paragraph 0354-0357
(2017/08/30)
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- A carbon nitride supported copper nanoparticle composite: a heterogeneous catalyst for the N-arylation of hetero-aromatic compounds
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A graphitic carbon nitride supported copper nanoparticle composite (Cu-gCN) has been found to be an active catalyst for the N-arylation of hetero-aromatic systems (pyrrole, pyrazole, and substituted indole) and benzamide molecules, with high product selectivity and good to excellent yields, using substituted aryl bromide as a coupling partner. The intercalated structure and the amine functional group of the carbon nitride prevent the aggregation of the catalytically active copper species during the reaction, and the recyclability study shows the stable performance of the catalyst without a significant loss of catalytic activity.
- Nandi, Debkumar,Siwal, Samarjeet,Mallick, Kaushik
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supporting information
p. 3082 - 3088
(2017/04/14)
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- Copper(I) Oxide/N,N′-Bis[(2-furyl)methyl]oxalamide-Catalyzed Coupling of (Hetero)aryl Halides and Nitrogen Heterocycles at Low Catalytic Loading
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An easily prepared oxalic diamide is a powerful ligand for the copper-catalyzed coupling of aryl halides with nitrogen heterocycles. Only 1–2 mol% each of copper(I) oxide and N,N′-bis[(2-furyl)methyl]oxalamide (BFMO) are needed to form N-arylation products under mild conditions. More than 10 different types of nitrogen heterocycles are compatible with these conditions, thereby giving the corresponding N-arylation products. (Figure presented.).
- Pawar, Govind Goroba,Wu, Haibo,De, Subhadip,Ma, Dawei
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supporting information
p. 1631 - 1636
(2017/05/22)
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- Magnetically recoverable copper nanorods and their catalytic activity in Ullmann cross-coupling reaction
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A novel polydentate ligand supported on Fe3O4@SiO2 was designed and demonstrated for the synthesis of Cu nanorods. The Fe3O4@SiO2/EP.EN.EG@Cu was characterized using X-ray diffraction, ther
- Rajabzadeh, Maryam,Eshghi, Hossein,Khalifeh, Reza,Bakavoli, Mehdi
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- Efficient and Mild Ullmann-Type N-Arylation of Amides, Carbamates, and Azoles in Water
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A simple, sustainable, efficient, mild, and low-cost protocol was developed for d-glucose-assisted Cu-catalyzed Ullmann reactions in water for amides, carbamates, and nitrogen-containing heterocycles. The reaction was compatible with diverse aryl/heteroaryl iodides, giving highly substituted pyridine, indole, or indazole rings. This method offers an attractive alternative to existing protocols, because the reaction proceeds in aqueous media, occurs at or near ambient temperature, and provides the N-arylated products in good to high yields.
- Bollenbach, Maud,Aquino, Pedro G. V.,de Araújo-Júnior, Jo?o Xavier,Bourguignon, Jean-Jacques,Bihel, Frédéric,Salomé, Christophe,Wagner, Patrick,Schmitt, Martine
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supporting information
p. 13676 - 13683
(2017/10/10)
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- A N - aryl pyrazole compounds and N - aryl imidazole compound of preparation method
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The invention discloses a preparation method of an N-arylpyrazole compound and an N-arylimidazole compound. The method comprises the following steps: reacting at 20-120 DEG C for 6-48 hours by taking aryl halide and pyrazole or imidazole as substrates and copper salt as a catalyst in an organic solvent in the presence of alkali and a nitrogenous ligand under nitrogen protection; and after the reaction is finished, separating and purifying a reaction liquid to obtain the N-arylpyrazole compound or the N-arylimidazole compound. A product prepared by utilizing the method disclosed by the invention can not only be directly used, but also be used for other reactions as a substrate and has the advantages of moderation in adopted reaction condition, simple operation step and post-processing process, high yield and suitability for large-scale production.
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Paragraph 0028; 0029; 0030; 0031; 0032; 0033
(2017/10/05)
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- PHOTOREDOX-CATALYZED DIRECT C-H FUNCTIONALIZATION OF ARENES
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The invention generally relates to methods of making substituted arenes via direct C-H amination. More specifically, methods of making para- and ortho-substituted arenes via direct C-H amination are disclosed. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present invention.
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-
Paragraph 00324; 00370
(2017/01/31)
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- A 1,10-phenanthrene rowling-N-Monoxide derivatives ligand and its application
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The invention relates to a 1,10-Phenanthroline monohydrate-dual N-monoxide derivative ligand. The derivative ligand has a structural formula as follows: FORMULA, wherein R1 and R8 are selected from hydrogen, halogen, hydroxyl, C1-C7 alkoxyl, straight-chain saturated or unsaturated C1-C6 alkyl, or branched-chain saturated or unsaturated C1-C6 alkyl; R2 to R7 are selected from hydrogen, halogen, hydroxyl, C1-C8 alkoxyl, straight-chain saturated or unsaturated C1-C6 alkyl, or branched-chain saturated or unsaturated C1-C6 alkyl, C3-C7 ring hydroxyl, benzyl, aryl or 5-7 membered heterocyclic ring. Hetero atoms (such as O or N) are contained in the ligand disclosed by the invention, and a transitional six-membered ring is formed through coordination with copper ions, so that aryl iodide, aryl bromide or aryl chloride is promoted to carry out a C-N coupling reaction with aliphatic amine or secondary aliphatic cyclammonium or aliphatic acid or nitrogen-containing heterocyclic compounds at room temperature.
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Paragraph 0198-0209
(2016/11/21)
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- N-terminal strategy (N1-N4) toward high performance liquid crystal materials
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Liquid crystal materials have a variety of applications in many fields such as display techniques as well as photonics and optics. However, only few design principles have been disclosed on liquid crystal materials with different N-heterocycles as the terminal groups, which hinder the development of the heterocyclic liquid crystals. Here, a strategy of molecular design for N-heterocyclic liquid crystal materials is reported. On the basis of this strategy, a series of convenient N-heterocycles such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, 1,2,3,4-tetrazole were applied to synthesize the novel liquid crystals. Most of them have proved to exhibit good mesomorphic behaviors which make them excellent components in the mixture of the LCDs materials. The simple attachment of N-heterocyclic units to the liquid crystal molecules through a mild reaction condition will provide a good prospect for the design of N-heterocyclic liquid crystals.
- Hong, Fengying,Xia, Zhengce,Zhu, Dezhao,Wu, Hongxiang,Liu, Jianhui,Zeng, Zhuo
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supporting information
p. 1285 - 1292
(2017/02/15)
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- Ullmann reaction through ecocatalysis: Insights from bioresource and synthetic potential
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We report the elaboration of novel bio-sourced ecocatalysts for the Ullmann coupling reaction. Ecocatalysis is based on the recycling of metals issued from phytoremediation or rehabilitation, and an innovative chemical valorization of the subsequent biomass in the field of catalysis. Here, we describe efficient copper accumulation by plants via phytoextraction and rhizofiltration. These phytotechnologies were revisited to demonstrate a novel potential of these natural resources for green chemistry. Taking advantage of the remarkable ability of the selected plants to accumulate Cu(ii) species into their roots or leaves, the latter can be directly used for the preparation of ecocatalysts, called Eco-Cu. The formed Eco-Cu catalysts are thoroughly characterized via ICP-MS, IR studies of pyridine sorption/desorption, TEM, XRD, SM and model reactions, in order to elucidate the chemical composition and catalytic activity of these new materials. Significant differences of properties and activities were observed between Eco-Cu and conventional Cu catalysts. Eco-Cu are highly active catalysts in Ullmann coupling reactions with lower Cu quantities compared to known copper catalysts.
- Clavé, Guillaume,Garel, Claire,Poullain, Cyril,Renard, Brice-Lo?c,Olszewski, Tomasz K.,Lange, Bastien,Shutcha, Mylor,Faucon, Michel-Pierre,Grison, Claude
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p. 59550 - 59564
(2016/07/06)
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- Ethylene glycol, an efficient and recoverable medium for copper-catalyzed N-arylation of diazoles under microwave irradiation
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Ethylene glycol was used as an efficient and recoverable medium for the reaction of diazoles with aryl iodides and aryl bromides in the presence of CuCl2 as the catalyst and K2CO3 as the base. Consequently, imidazole, benzimidazole, and pyrazole reacted readily under microwave irradiation to give good to excellent yields of their corresponding N-arylated products in relatively short time periods. Apparently, ethylene glycol plays a dual role by activating the catalyst and also providing a homogenous medium for the processes. The reaction medium consisting of the solvent, the base, and the copper salt was recovered and reused successfully in the next several reactions.
- Sharifi, Ali,Ghonouei, Nima,Abaee, M. Saeed
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supporting information
p. 249 - 256
(2016/03/09)
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- N-Picolinamides as ligands for Ullmann-type C-N coupling reactions
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The use of N-phenyl-2-pyridincarboxamide-1-oxide as a ligand with Cu2O in Ullmann type C-N bond formations between aryl halides and N-heteroaryls in common solvents, such as MeCN, DMF, and DMSO at 82-120 °C has been successfully demonstrated. The ligand is effective when only 4% equiv is used relative to the substrate. The reaction provided the corresponding products in coupling of electron-rich, electron poor, and ortho-substituted aryl halides, including ortho aryl-chlorides, in good to very good yields. N-arylation is selectively preferred at the benzyl position when ortho-halide benzyl bromide is reacted with one equivalent of pyrazole. However, di-N-arylation is achieved in very high yields when 2.5 equiv of pyrazole is used, providing a stoichiometric control over the coupling reaction.
- Damkaci, Fehmi,Alawaed, Abdulkhaliq,Vik, Erik
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supporting information
p. 2197 - 2200
(2016/05/02)
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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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supporting information
p. 245 - 252
(2015/10/29)
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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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- Facile Synthesis of 1-Arylpyrazoles
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A convenient and transition-metal-free synthesis of 1-arylpyrazoles that involves the cycloaddition of 3-arylsydnones and acrylic acid is presented. The process proceeds smoothly to obtain the target products with moderate to high yields.
- Yang, Yiwen,Kuang, Chunxiang
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supporting information
p. 2281 - 2284
(2015/08/03)
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- Directing/Protecting-Group-Free Synthesis of Tetraaryl-Substituted Pyrazoles through Four Direct Arylations on an Unsubstituted Pyrazole Scaffold
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A directing/protecting-group-free synthesis of 1,3,4,5-tetraaryl-substituted pyrazoles was achieved through four transition metal-catalyzed direct arylations. Various pyrazoles with four different aryl rings were obtained using readily available reagents from an unsubstituted pyrazole. Two aryl-substituted pyrazoles showed intense violet fluorescence, high quantum yields (Φf=0.68, 0.64), and large Stokes shifts (19000, 15200cm-1).
- Fuse, Shinichiro,Morita, Taiki,Johmoto, Kohei,Uekusa, Hidehiro,Tanaka, Hiroshi
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supporting information
p. 14370 - 14375
(2015/10/05)
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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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- Catalytic activity and antibacterial properties of nanopolymer-supported copper complex for C-N coupling reactions of amines and nitrogen-containing heterocycles with aryl halides
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This paper reports on the antibacterial properties and application of nanopolymer-supported copper complex for the ligand-free C-N coupling reactions of amines and nitrogen-containing heterocycles with aryl halides. This method has the advantages of high yields, simple methodology, and easy workup. The catalyst can be recovered by simple filtration from the reaction mixture and reused several times without significant loss of catalytic activity.
- Nasrollahzadeh, Mahmoud,Zahraei, Ali,Pourbasheer, Eslam
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p. 1329 - 1334
(2015/08/18)
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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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p. 6360 - 6363
(2015/11/16)
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- Ligand-free N-arylation of heterocycles using metal-organic framework [Cu(INA)2] as an efficient heterogeneous catalyst
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A metal-organic framework [Cu(INA)2] was synthesized and used as a heterogeneous catalyst for arylation of a wide range of N-H heterocycles and aryl halides under ligand-free conditions. The N-arylation reaction involved the use of 5 mol% Cu-MOF catalyst with K3PO4 or tBuOLi as the base in dimethylacetamide (DMA) solvent at 100 °C in 6 h. [Cu(INA)2] exhibited higher catalytic activity for the N-arylation transformation than that of common homogeneous copper catalysts and other Cu-MOFs with unsaturated open metal sites such as Cu2(BDC)2(BPY), Cu3(BTC)2, and Cu2(BDC)2(DABCO). Interestingly, reaction conditions are compatible with a wide range of N-H heterocycles, functional groups, and aryl chlorides. A leaching test indicated no contribution of leached active species in the reaction filtrate. Furthermore, the [Cu(INA)2] catalyst could be facilely separated from the reaction mixture and recovered and reused several times without a significant degradation in catalytic activity.
- Truong, Thanh,Nguyen, Chi V.,Truong, Ngoc T.,Phan, Nam T. S.
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p. 107547 - 107556
(2016/01/09)
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- Copper-catalyzed arylation of nitrogen heterocycles from anilines under ligand-free conditions
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The arylation of pyrazole and derivatives can be achieved by coupling arenediazonium species (formed in situ from anilines) by using a catalytic system that employs low-toxicity and inexpensive copper metal under very mild and ligand-free conditions (T = 20 ° C). From other nitrogen heterocycles, the presence of an additive (NBu4I) significantly improves the efficiency of the catalytic system. These results represent the first examples of C-N bond formation from arenediazonium species.
- Toummini, Dounia,Tlili, Anis,Bergs, Julien,Ouazzani, Fouad,Taillefer, Marc
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supporting information
p. 14619 - 14623
(2015/01/09)
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- Ruthenium-catalyzed c-h silylation of 1-arylpyrazole derivatives and fluoride-mediated carboxylation: Use of two nitrogen atoms of the pyrazole Group
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Carboxylation of 1-arylpyrazole derivatives was developed using a ruthenium-catalyzed ortho silylation in conjunction with fluoride-mediated carboxylation with carbon dioxide. The two nitrogen atoms of pyrazole play crucial roles in promoting ortho silylation via the formation of a five-membered ruthenacycle and in accelerating aryl anion formation by lowering the electron density of the aromatic ring. Georg Thieme Verlag Stuttgart New York.
- Mita, Tsuyoshi,Tanaka, Hiroyuki,Michigami, Kenichi,Sato, Yoshihiro
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supporting information
p. 1291 - 1294
(2014/06/10)
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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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supporting information
p. 3049 - 3051
(2014/05/20)
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- Aromatic N-arylations catalyzed by copper-anchored porous zinc-based metal-organic framework under heterogeneous conditions
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A highly porous Zn-based metal-organic framework (MOF) IRMOF-3 was covalently decorated with pyridine-2-aldehyde. The free amine group of IRMOF-3 upon condensation with pyridine-2-aldehyde affords a bidentate Schiff-base moiety in the porous matrix. The Schiff base moieties are availed to anchor copper(II) ions to display the catalyst's utility towards catalytic reactions. The catalyst was characterized by UV/Vis and IR spectroscopy, powder XRD spectrometry, SEM energy-dispersive X-ray spectrometry, and nitrogen sorption measurements. The catalyst exhibits excellent activity in catalyzing the N-arylation reaction of nitrogen-containing heterocycles with aryl bromides in DMSO medium, under mild condition (90°C) in the presence of Cs 2CO3. The porous catalyst demonstrates size selectivity towards substrate as a result of the presence of active sites inside the pores of the MOF. The anchored complex seems to be not leached or decomposed during the catalytic reactions up to five successive catalytic cycles, demonstrating practical advantages over homogeneous catalysis.
- Maity, Tanmoy,Saha, Debraj,Koner, Subratanath
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p. 2373 - 2383
(2014/08/18)
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- New ligands for copper-catalyzed C-N coupling reactions at gentle temperature
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Pyridin-2-ol-N-oxide was designed as an efficient ligand for the coupling reaction of aryl iodides, aryl bromides and aryl chlorides, respectively, with primary amines, cyclic secondary amines or N-containing heterocycles at room or moderate temperature. The catalytic system showed great functional groups tolerance and excellent selective reactivity.
- Su, Jinyue,Qiu, Yatao,Jiang, Sheng,Zhang, Dayong
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supporting information
p. 685 - 688
(2014/10/15)
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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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p. 775 - 778
(2014/06/09)
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- N-arylation of heterocycles catalyzed by activated-copper in pure water
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N-arylation Activated-copper powder is an efficient catalyst for the N-arylation of heterocycles with aryl halides and can be reused several times. The reactions can proceed smoothly in water by using LiOH as base and give the corresponding products in good yields. The protocol shows good tolerance toward various functional groups.
- Yang, Qichao,Wang, Yufang,Lin, Dong,Zhang, Mingjie
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supporting information
p. 1994 - 1997
(2013/04/10)
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- N-Arylation of heterocycles promoted by tetraethylenepentamine in water
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Tetraethylenepentamine and triethylenetetramine are found to be efficient organic bases for the N-arylation of pyrazole and imidazole with aryl and heteroaryl-iodides and -bromides catalyzed by CuI in water at moderate temperature. The cross-couplings proceed smoothly with good to excellent yields and a variety of functional groups are tolerated under this condition.
- Yang, Qichao,Wang, Yufang,Yang, Li,Zhang, Mingjie
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supporting information
p. 6230 - 6233
(2013/07/19)
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- Ruthenium-catalyzed C-H functionalization of arylpyrazoles: Regioselective acylation with acid chlorides
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A ruthenium-catalyzed C-H acylation of arylpyrazoles with a variety of acyl chlorides is described. The acylation reaction exhibits good regioselectivity and both aromatic and aliphatic acyl chlorides can be effectively coupled to the arylpyrazoles at the
- Liu, Po Man,Frost, Christopher G.
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supporting information
p. 5862 - 5865
(2013/12/04)
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- Salen-Cu(II) complex catalysed N-arylation of pyrazole under mild conditions
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Three inexpensive and air-/moisture-stable complexes (Salden)Cu (Salden = N, N'-bis(salicylidene)-1,2-dimethylethylenediamine), (Saldch)Cu (Saldch = N, N'-bis(salicylidene)-1,2-cyclohexenediamine), and (Salph)Cu (salph = N, N'-bis(salicylidene)-1,2-phenylenediamine) were synthesised and evaluated as catalysts for the N-arylation of pyrazole with aryl halides. A variety of aryl iodides and bromides underwent coupling with pyrazole, promoted by the (Saldch)Cu complex, in moderate to excellent yields without the protection by an inert gas.
- Liu, Yan,Liu, Wei,Zhang, Qin,Liu, Ping,Xie, Jian-Wei,Dai, Bin
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p. 636 - 637
(2013/11/06)
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