- A Pd/Cu-Free magnetic cobalt catalyst for C-N cross coupling reactions: synthesis of abemaciclib and fedratinib
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Herein, the synthesis of a nano-catalytic system comprising magnetic nanoparticles as the core and edible natural ligands bearing functional groups as supports for cobalt species is described. Subsequent to its characterization, the efficiency of the catalyst was investigated for C-N cross-coupling reactions using assorted derivatives of amines and aryl halides. This novel and easily accessible Pd- and Cu-free catalyst exhibited good catalytic activity in these reactions using γ-valerolactone (GVL) at room temperature; good recyclability bodes well for the future application of this strategy. The introduced catalytic system is attractive in view of the excellent efficiency in an array of coupling reactions and its versatility is illustrated in the synthesis of abemaciclib and fedratinib, which are FDA-approved new and significant anti-cancer medicinal compounds that are prepared under green reaction conditions.
- Hajipour, Abdol R.,Khorsandi, Zahra,Sarfjoo, Mohamad Reza,Varma, Rajender S.
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supporting information
p. 5222 - 5229
(2021/07/29)
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- Palladium-Catalyzed Cyanation of Aryl Halides Using Formamide and Cyanuric Chloride as a New “CN” Source
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A new source of “CN” employing formamide and cyanuric chloride is introduced for the cyanation reactions. The treatment of formamide and 2,4,6-trichloro-1,3,5-triazine (TCT; cyanuric chloride) afforded an efficient cyanating agent which it can be used as a nontoxic, readily available, and non-expensive reagent in the cyanation transformations. In this study, palladium-catalyzed cyanation of aryl halides was successfully accomplished using this new “CN” source in high yields.
- Niknam, Esmaeil,Panahi, Farhad,Khalafi-Nezhad, Ali
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p. 2699 - 2707
(2020/04/08)
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- Exploration of Catalytic Activity of Quercetin Mediated Hydrothermally Synthesized NiO Nanoparticles Towards C–N Coupling of Nitrogen Heterocycles
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Abstract: A new approach towards the preparation of phase pure NiO nanoparticles via quercetin mediated hydrothermal method is proposed in this work. The performance of quercetin as capping agent is found to be good. The XRD and SEM results confirm that the NiO nanoparticles prepared with quercetin are smaller in size and have refined morphology than that prepared without quercetin. Thermal stability, elemental composition and particle size of prepared nanoparticles have been revealed by TG-DSC, EDAX and HR-TEM analysis respectively. N2 adsorption–desorption isotherm (BET) analysis was done to reveal specific surface area. The prepared NiO nanoparticles act as cost effective, environmental friendly and efficient catalyst for the C–N cross coupling of indole and electron deficient pyrrole, under very mild reaction conditions. The catalytic system is able to tolerate many functional groups with different electronic and structural properties. Hence the present catalytic system may be possibly applied in large scale synthesis. Graphic Abstract: [Figure not available: see fulltext.].
- Krishnaveni,Lakshmi,Kadirvelu,Kaveri
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p. 1628 - 1640
(2019/12/24)
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- Nickel-catalyzed decarbonylation of: N -acylated N-heteroarenes
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Nickel-catalyzed decarbonylation of N-acylated N-heteroarenes is developed. This method can be used to produce a variety of N-aryl heteroarenes, including pyrroles, indoles, carbazoles and phenoxazines, using benzoic acid derivatives as arylating reagents. Arylnickelamide intermediates that are relevant to the catalytic reaction were characterized by X-ray crystallography. When N-acylated benzimidazoles are used as substrates, decarbonylation accompanied 1,2-migration to form 2-arylated benzimidazoles.
- Morioka, Toshifumi,Nakatani, Syun,Sakamoto, Yuki,Kodama, Takuya,Ogoshi, Sensuke,Chatani, Naoto,Tobisu, Mamoru
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p. 6666 - 6671
(2019/07/17)
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- Copper-Catalyzed Decarboxylative N -Arylation of Indole-2-carboxylic Acids
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A novel decarboxylative N -arylation of indole-2-carboxylic acids with aryl halides is developed. The reaction proceeds efficiently in the presence of Cu 2 O as the catalyst to give the corresponding N -aryl indoles in high yields. This synthet
- Zhang, Yan,Hu, Zhe-Yao,Li, Xin-Chang,Guo, Xun-Xiang
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p. 1803 - 1808
(2019/04/05)
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- Nickel-Catalyzed C-N Cross-Coupling of Ammonia, (Hetero)anilines, and Indoles with Activated (Hetero)aryl Chlorides Enabled by Ligand Design
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The Ni(II) precatalyst (C1) featuring the phosphonite ancillary ligand Phen-DalPhos (L1) was employed in the cross-coupling of (hetero)anilines with (hetero)aryl chlorides and in the diarylation of ammonia with (hetero)aryl chlorides to afford heteroatom-dense di(hetero)arylamines. The PAd2-DalPhos precatalyst C4 provided complementary reactivity in cross-couplings of indoles with (hetero)aryl chlorides. Taken together, the demonstration of room-temperature reactivity within each of the reaction classes examined and the observation of useful chemoselectivity at low loading (≤0.5 mol % Ni) and on gram-scale distinguishes C1 and C4 from other metal catalysts (i.e., copper, palladium, nickel, or other) within the field of C-N cross-coupling chemistry.
- McGuire, Ryan T.,Paffile, Julia F. J.,Zhou, Yuqiao,Stradiotto, Mark
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p. 9292 - 9297
(2019/10/11)
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- Bulky 1,1′-Ferrocenyl Ligands Featuring Diazaphospholene or Dioxaphosphepine Donor Fragments: Catalytic Screening in Nickel-Catalyzed C-N Cross-Coupling
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1,1′-Ferrocenyl ligands featuring either bulky dioxaphosphepine (L1) or diazaphospholene (L2) donor moieties have been prepared, crystallographically characterized, and tested in representative nickel-catalyzed C–N cross-coupling reactions. Ligand L1 prov
- McGuire, Ryan. T.,Clark, Jillian S. K.,Gatien, Alexandre V.,Shen, M. Yue,Ferguson, Michael J.,Stradiotto, Mark
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p. 4112 - 4116
(2019/11/02)
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- Formation of C-C, C-S and C-N bonds catalysed by supported copper nanoparticles
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Transition-metal catalysed cross-coupling reactions are still dominated by palladium chemistry. Within the recent past, copper has gained ground against palladium by virtue of its cheaper price and equivalent function in certain reactions. Four catalysts consisting of copper nanoparticles on zeolite, titania, montmorillonite and activated carbon have been tested in three palladium- and ligand-free cross-coupling reactions to form carbon-carbon, carbon-sulfur and carbon-nitrogen bonds. CuNPs/zeolite has been found to be the best one in the Sonogashira reaction of aryl iodides and arylacetylenes, as well as in the coupling of aryl halides with aryl and alkyl thiols, being reusable in both cases. However, the arylation of nitrogen-containing heterocycles (imidazole, pyrazole, benzimidazole and indole) has been better accomplished with CuNPs/titania, albeit CuNPs/activated carbon showed better recycling properties. The catalytic activity of the nanostructured catalysts has been compared with that of twelve commercial copper catalysts, with the former outperforming the latter in the three types of reactions studied.
- Mitrofanov, Alexander Yu.,Murashkina, Arina V.,Martín-García, Iris,Alonso, Francisco,Beletskaya, Irina P.
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p. 4401 - 4412
(2017/10/13)
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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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- Evaluating 1,1′-Bis(phosphino)ferrocene Ancillary Ligand Variants in the Nickel-Catalyzed C-N Cross-Coupling of (Hetero)aryl Chlorides
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Previous reports in the literature have established the utility of 1,1′-bis(diphenylphosphino)ferrocene (DPPF, LPh) in the nickel-catalyzed cross-coupling of (hetero)aryl electrophiles with primary or secondary amines. In an effort to evaluate
- Clark, Jillian S. K.,Voth, Christopher N.,Ferguson, Michael J.,Stradiotto, Mark
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p. 679 - 686
(2017/04/21)
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- Thieme Chemistry Journals Awardees - Where Are They Now? Efficient Cross-Coupling of Secondary Amines/Azoles and Activated (Hetero)Aryl Chlorides Using an Air-Stable DPEPhos/Nickel Pre-Catalyst
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Synthesis and characterization of the new air-stable pre-catalyst (DPEPhos)Ni(2-mesityl)Br (C1) is reported, along with the application of this pre-catalyst in the cross-coupling of secondary amines/azoles with activated (hetero)aryl chlorides to afford t
- Sawatzky, Ryan S.,Ferguson, Michael J.,Stradiotto, Mark
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supporting information
p. 1586 - 1591
(2017/08/11)
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- Magnetically retrievable lepidocrocite supported copper oxide nanocatalyst (Fe-CuO) for N-arylation of imidazole
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A simple and efficient lepidocrocite-supported copper oxide catalyst (Fe-CuO) has been successfully prepared by a simple precipitation method in aqueous medium from readily available inexpensive starting materials and was used as a heterogeneous nanocatal
- Sivakami,Babu, S. Ganesh,Dhanuskodi,Karvembu
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p. 8571 - 8578
(2015/03/03)
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- MCM-41-immobilized bidentate nitrogen copper(I) complex: A highly efficient and recyclable catalyst for Buchwald N-arylation of indoles
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The heterogeneous N-arylation reaction of indoles with aryl halides was achieved in toluene at 110 C by using 4 mol % MCM-41-immobilized bidentate nitrogen copper(I) complex [MCM-41-2N-CuI] as catalyst and K3PO 4 as base, yielding a variety of N-arylindoles in good to excellent yields. The heterogeneous copper catalyst exhibited as high activity as homogeneous CuI/diamine catalytic system and can be easily prepared by a simple two-step procedure from commercially available and cheap reagents and recovered by a simple filtration of the reaction solution and reused for 10 cycles with almost consistent activity.
- Xiao, Ruian,Zhao, Hong,Cai, Mingzhong
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p. 5444 - 5450
(2013/06/27)
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- PEG3400-Cu2O-Cs2CO3: an efficient and recyclable microwave-enhanced catalytic system for ligand-free Ullmann arylation of indole and benzimidazole
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A mild, simple and efficient microwave-enhanced copper-catalyzed protocol for N-arylation using high molecular weight poly(ethylene glycol) (PEG3400) as a solvent is reported. Indole and benzimidazole have been N-arylated in the presence of cup
- Colacino, Evelina,Villebrun, Laurent,Martinez, Jean,Lamaty, Frédéric
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experimental part
p. 3730 - 3735
(2010/07/05)
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- One-Pot N-Arylation of indoles directly from N-arylsulfonylindoles via consecutive deprotection and SnAr reactions with activated aryl halides
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An efficient one-pot step by step t-BuOK-mediated procedure for the synthesis of N-arylindoles has been developed in moderate to good yields. The protocol involves the consecutive deprotection of N-arylsulfonylindoles as latent indoles and subsequent SnAr
- Xu, Hui,Fan, Ling-Ling
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experimental part
p. 321 - 323
(2009/11/30)
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- N-arylation of heterocycles with activated chloro- and fluoroarenes using nanocrystalline copper(II) oxide
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Nanocrystalline copper oxide was found to be an effective heterogeneous catalyst for the N-arylation of heterocycles with activated chloro- and fluoroarenes using potassium carbonate as base. N-Arylated products were isolated in good to excellent yields. The catalyst can be used for five cycles with almost consistent activity.
- Kantam, M. Lakshmi,Yadav, Jagjit,Laha, Soumi,Sreedhar, Bojja,Jha, Shailendra
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p. 1938 - 1942
(2008/09/16)
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- Method for arylating aza-heterocycles with activated aromatic compounds in the presence of caesium carbonate
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The invention concerns a process for the preparation of N-aryl-aza-heterocycles of the general formula I by reaction of aza-heterocycles with activated aryl halides with use of caesium carbonate without addition of further catalysts at room temperature.
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Page column 7
(2008/06/13)
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- SUBSTITUTED ANILINIC PIPERIDINES AS MCH SELECTIVE ANTAGONISTS
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This invention is directed to compounds which are selective antagonists for melanin concentrating hormone-1 (MCH1) receptors. The invention provides a pharmaceutical composition comprising a therapeutically effective amount of the compound of the invention and a pharmaceutically acceptable carrier. This invention provides a pharmaceutical composition made by combining a therepeutically effective amount of the compound of this invention and a pharmaceutically acceptable carrier. This invention further provides a process for making a pharmaceutical composition comprising combining a therapeutically effective amount of the compound of the invention and a pharmaceutically acceptable carrier.
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Page column 207
(2010/02/06)
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- Direct C-H bond arylation: Selective palladium-catalyzed C2-arylation of N-substituted indoles
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(Equation Presented) We present a new, practical method by which N-substituted indoles may be selectively arylated in the C2-position with good yields, low catalyst loadings, and a high degree of functional group tolerance. Our investigation found that two competitive processes, namely, the desired cross-coupling and biphenyl formation, were operative in this reaction. A simple kinetic model was formulated that proved to be instructive and provided useful guidelines for reaction optimization; the approach described within may prove to be useful in other catalytic cross-coupling processes.
- Lane, Benjamin S.,Sames, Dalibor
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p. 2897 - 2900
(2007/10/03)
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- A novel and selective method for the N-arylation of indoles mediated by KF/Al2O3
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Indole was reacted with aryl electrophiles in the presence of 37% KF/Al2O3 and catalytic 18-crown-6 in DMSO at 120°C to give selectively 1-arylindoles in fair to excellent yield. Electrophiles containing electronically unfavorable su
- Smith III, William J.,Sawyer, J. Scott
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p. 299 - 302
(2007/10/02)
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