- A facile and practical copper diacetate mediated, ligand free C-N cross coupling of trivalent organobismuth compounds with amines and N-heteroarenes
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In present work, an efficient Cu(OAc)2·H2O catalyzed protocol in the absence of any additional ligand has been developed for the N-arylation of amines and nitrogen containing heterocycles using trivalent organobismuth reagents under mild conditions. This protocol tolerates a variety of functional groups on amines and the organobismuth reagent with a high degree of chemoselectivity.
- Jadhav,Pardeshi
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- Iron-catalyzed oxidative monoarylation of primary amines with organozinc reagents
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The reaction of a primary zinc amide with a diorganozinc reagent gives a secondary amine in the presence of Fe(acac)3 as a catalyst and 1,2-dichloroisobutane (DCIB) as an oxidant. Halogen groups such as F, Cl, Br, and I are tolerated well. The dichloride oxidant and heat are essential to achieve the C-N bond formation presumably from a catalytic iron intermediate species bearing aryl and amido groups.
- Nakamura, Yuki,Ilies, Laurean,Nakamura, Eiichi
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- Addition of aryl cuprates to azides: a novel approach for the synthesis of unsymmetrical diaryl amines
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Aryl and benzyl azides react smoothly with aryl cuprates, generated in situ from aryl magnesium bromide and CuCN in THF to furnish a variety of unsymmetrical diaryl amines in good yields. This is the first report on the synthesis of diarylamines from aryl
- Yadav,Reddy, B.V. Subba,Borkar, Prashant,Reddy, P. Janardhan
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- CuCl2 heterogenized on metformine-modified polystyrene resin as an antibacterial agent and recyclable nanocatalyst for Ullmann-type C-N coupling reactions
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Merrifield Resin was functionalized with metformine and applied as a solid support to immobilize the CuCl2. The Ps-Met/CuCl2 was characterized by several techniques including Fourier transform infrared (FTIR), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), wavelength-dispersive X-ray spectroscopy (WDX) and inductively coupled plasma (ICP). The Ps-Met/CuCl2 was used as an efficient recyclable solid nanocatalyst for N-arylation of indole and aniline through coupling reactions of Ullmann-type C-N. The advantages of this method are easy workup, improved yields, and simple recovery via filtration. Ultimately, the Ps-Met/CuCl2 antibacterial property was examined against two bacteria (Staphylococcus aureus (Staph. aureus) and Escherichia coli (E. coli)) and indicated its antibacterial performance against gram negative (E. coli) bacteria and gram positive (Staph. aureus).
- Veisi, Hojat,Ahmadian, Hossein,Mirshokraie, Seyed Ahmad,Didehban, Khadijeh,Zangeneh, Mohammad Mahdi
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- Synthesis, characterization and catalytic application of some novel binuclear transition metal complexes of bis-(2-acetylthiophene) oxaloyldihydrazone for CN bond formation
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In the present work, synthesis, characterization and catalytic properties of some novel complexes derived from a Schiff base bis-(2-acetylthiophene) oxaloyldihydrazone with various transition metal ions and precursors have been reported. The complexes were characterized by IR, NMR, ESR, electronic and mass spectroscopy, magnetic moments and TGA studies. Molecular structures of the ligand and its Cu(I) complex are determined by single crystal X-ray diffraction. Electronic spectral studies exhibit a 6-coordinated geometry around metal centers for Co(II), Ni(II) and Cu(II) complexes, whereas 4-coordinated geometry for Cu(I) and Zn(II) complexes. ESR spectra indicate a distorted octahedral geometry for Cu(II) complex in DMSO frozen solution. The electro-chemical studies of Ni(II) and Cu(II) complexes reveal a metal based reversible redox behavior. The catalytic activity of the complexes has been demonstrated for the cross-coupling of arylboronic acids with various N-nucleophiles. Ni(II) complex exhibited the maximum impact on catalytic activity with the product yields ranging from 62% to 82%.
- Singh, Divya Pratap,Raghuvanshi, Dushyant S.,Singh,Singh, Vinod P.
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- Cu2(BDC)2(BPY)-MOF: An efficient and reusable heterogeneous catalyst for the aerobic Chan-Lam coupling prepared via ball-milling strategy
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Nanoporous Cu2(BDC)2(BPY)-MOF was used as efficient and reusable heterogeneous catalyst to effect the aerobic cross-coupling of aromatic amines and phenyl boronic acid (Chan-Lam coupling). Ball-milling strategy was utilized for the first as a powerful green and energy-efficient method for the synthesis of this nanoporous metal-organic framework. Certain ratio of metal ion and organic linkers were held to improve the quality of nanostructures. Cu2(BDC)2(BPY) were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET) surface area analysis.
- Khosravi, Armaqan,Mokhtari, Javad,Naimi-Jamal, Mohammad Reza,Tahmasebi, Sharareh,Panahi, Leila
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- A Novel Modified Cross-Coupling of Phenols and Amines Using Dichloroimidazolidinedione (DCID)
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Phenols are considered as an ideal alternative to aryl halides as coupling partners in cross-coupling reactions. In the present work a copper-catalyzed cross-coupling of phenols with various aromatic and aliphatic amines for the synthesis of secondary aryl amines using dichloroimidazolidinedione (DCID) as a new and efficient activating agent has been developed. Substituted phenols were compatible with the standard reaction conditions. The two proposed mechanisms, which are based on the oxidation addition of copper with Ar-OMCID (MCID: Monochloroimidazolidinedione), are also discussed.
- Madankar, Kamelia,Mokhtari, Javad,Mirjafary, Zohreh
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- N-Arylation of indole and aniline by a green synthesized CuO nanoparticles mediated by Thymbra spicata leaves extract as a recyclable and heterogeneous nanocatalyst
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In a biological procedure where the aqueous leaves extract of Thymbra spicata was utilized as a reducing and capping agent, copper oxide (CuO) nanoparticles (NPs) were synthesized. These CuO NPs were characterized via Fourier transformed infrared spectroscopy (FT-IR), X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), wavelength-dispersive X-ray spectroscopy (WDX), and UV–visible spectroscopy. The as prepared nanoparticles have been employed as an appropriate nanocatalyst for ligand-free N-arylation of indole and aniline via Ullmann-type C[sbnd]N coupling reactions. Adequate to outstanding quantities of the N-arylated products were synthesized and the nanocatalyst was retrievable and reusable seven times without noticeable decrease in catalytic performance.
- Veisi, Hojat,Hemmati, Saba,Javaheri, Hadis
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- Copper nanoparticle anchored biguanidine-modified Zr-UiO-66 MOFs: a competent heterogeneous and reusable nanocatalyst in Buchwald-Hartwig and Ullmann type coupling reactions
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We have designed a functionalized metal-organic framework (MOF) of UiO topology as a support, with an extremely high surface area, adjustable pore sizes and stable crystalline coordination polymeric structure and implanted copper (Cu) nanoparticles thereon. The core three dimensional Zr-derived MOF (UiO-66-NH2) was modified with a biguanidine moiety following a covalent post-functionalization approach. The morphological and physicochemical features of the material were determined using analytical methods such as FT-IR, SEM, TEM, EDX, atomic mapping, XRD and ICP-OES. The SEM and XRD results justified the unaffected morphology of Zr-MOF after structural modifications. The as-synthesized UiO-66-biguanidine/Cu nanocomposite was catalytically explored in the aryl and heteroaryl Buchwald-Hartwig C-N and Ullmann type C-O cross coupling reactions with excellent yields. A library of biaryl amine and biaryl ethers was synthesized over the catalyst under mild and green conditions. Furthermore, the catalyst was isolated by centrifugation and recycled 11 times with no significant copper leaching or change in its activity.
- Veisi, Hojat,Neyestani, Narges,Pirhayati, Mozhgan,Ahany Kamangar, Sheida,Lotfi, Shahram,Tamoradi, Taiebeh,Karmakar, Bikash
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p. 22278 - 22286
(2021/07/02)
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- A quinoxaline-based porous organic polymer containing copper nanoparticles CuNPs@Q-POP as a robust nanocatalyst toward C-N coupling reaction
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A novel porous organic polymer (denoted by Q-POP) was successfully fabricated by free-radical copolymerization of allyl-substituted 2,3-di(2-hydroxyphenyl)1,2-dihydroquinoxaline, and divinylbenzene under solvothermal conditions and used as a new platform for immobilization of copper nanoparticles. The CuNPs@Q-POP nanocatalyst was prepared via incorporating of Cu(NO3)2 into the polymeric network, followed by the reduction of Cu2+ ion with hydrazine hydrate. The obtained materials were characterized through FT-IR, XRD, N2 adsorption-desorption isotherms, ICP, TGA, SEM, HR-TEM, EDX, and the single-crystal X-ray crystallography. The results displayed that Q-POP and CuNPs@Q-POP possessed high surface area, hierarchical porosity, and excellent thermal and chemical stability. The as-synthesized catalyst was utilized for the Ullmann C-N coupling reaction of aromatic amines and different aryl halides to prepare various diarylamine derivatives. All types of aryl halides (except aryl fluorides) were screened in the Ullmann C-N coupling reaction with aromatic amines to produce diaryl amines in good to excellent yields (50-98%), and it turned out that aryl iodides have the best results. Besides, due to the strong interactions between CuNPs, N, and O-atoms of quinoxaline moiety existing in the polymeric framework, the copper leaching from the support was not observed. Furthermore, the catalyst was recycled and reused for five consecutive runs without significant activity loss.
- Gorginpour, Forough,Zali-Boeini, Hassan,Rudbari, Hadi Amiri
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p. 3655 - 3665
(2021/02/03)
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- Schiff bases-titanium (III) & (IV) complex compounds: Novel photocatalysts in Buchwald-Hartwig C–N cross-coupling reaction
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Nine novel Schiff bases were derived from salicylic aldehyde and oxalic aldehyde, isolated, and their molecular and spatial structure were explored by a set of experiments (IR, CNMR, HNMR, CHN, SEM, XRD) and theoretical simulation (DFT def2-TZVP). A high potential was predicted in metal cations chelating. The isolated organic species were applied as the ligands in the reaction of complex formation with titanium (III) chloride and (IV) bromide and 12 novel complexes were synthesized and studied experimentally and theoretically. Using the UV–vis spectroscopic titration, the solution stability of the complexes was indicated. Depending on the nature of the Schiff base ligand, their formation constants were calculated in the range of 6.84–17.32. Using the DFT def2-TZVP theoretical method together with the experimental spectroscopic data, the coordination types of the ligands were investigated, and the structure of the complexes was proposed. The photocatalytic ability of the isolated complexes was tested in the C-N cross-coupling reaction under sunlight. Complexes exhibited high visible-light photocatalytic activity for a wide range of aromatic and benzylic amines including electron-withdrawing and electron-donating groups from moderate to good yields ranging in 50–85 %. The use of an inexpensive, clean, and renewable energy source (visible light) is the superiority of the developed photocatalytic systems.
- Absalan, Yahya,Ghandi, Khashayar,Gholizadeh, Mostafa,Kovalchukova, Olga,Mahmoudi, Ghodrat,Sarvestani, Hossein Sabet,Shad, Nazanin Noroozi,Strashnov, Pavel
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- Chitosan nanoparticles functionalized poly-2-hydroxyaniline supported CuO nanoparticles: An efficient heterogeneous and recyclable nanocatalyst for N-arylation of amines with phenylboronic acid at ambient temperature
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The present study aims to prepare an effective and eco-friendly nanocatalyst for the Chan–Lam coupling reaction of phenylboronic acid and amine in aerobic conditions. For this purpose, chitosan was extracted from shrimp shells waste by demineralization, deproteinization, and deacetylation processes and then converted to chitosan nanoparticles (CSN) by the ionic gelation with tripolyphosphate anions. Afterward, poly-2-hydroxyaniline (P2-HA) was grafted to chitosan nanoparticles (NPs) to employ as the support for CuO NPs. Characterization of the nanocatalyst was done using Fourier transform infrared (FT-IR), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), mapping, energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The CuO NPs were identified in the spherical shape with an average size of 17 nm. The prepared nanocatalyst exhibited excellent catalytic performance with a high turnover number (TON) and turnover frequency (TOF) for the Chan–Lam coupling reaction of phenyl boronic acid and amines with different electronic properties. The prepared catalyst could be readily recovered and reused for at least five runs without any noticeable change in structure and catalytic performance. Chitosan (CS) was prepared via demineralization, deproteinization, and deacetylation of shrimp shell and chitosan nanoparticles (CSN) were prepared via ionic gelation process. Polymerization of 2-HA on the CSN surface was done to increase functional groups and create active sites for CuO NPs attachments. CuO NPs-P2-HA-CSN nanocomposite has been shown high efficiently for the Chan–Lam coupling reaction.
- Seyedi, Neda,Zahedifar, Mahboobeh
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- Mediator-Enabled Electrocatalysis with Ligandless Copper for Anaerobic Chan-Lam Coupling Reactions
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Simple copper salts serve as catalysts to effect C-X bond-forming reactions in some of the most utilized transformations in synthesis, including the oxidative coupling of aryl boronic acids and amines. However, these Chan-Lam coupling reactions have historically relied on chemical oxidants that limit their applicability beyond small-scale synthesis. Despite the success of replacing strong chemical oxidants with electrochemistry for a variety of metal-catalyzed processes, electrooxidative reactions with ligandless copper catalysts are plagued by slow electron-transfer kinetics, irreversible copper plating, and competitive substrate oxidation. Herein, we report the implementation of substoichiometric quantities of redox mediators to address limitations to Cu-catalyzed electrosynthesis. Mechanistic studies reveal that mediators serve multiple roles by (i) rapidly oxidizing low-valent Cu intermediates, (ii) stripping Cu metal from the cathode to regenerate the catalyst and reveal the active Pt surface for proton reduction, and (iii) providing anodic overcharge protection to prevent substrate oxidation. This strategy is applied to Chan-Lam coupling of aryl-, heteroaryl-, and alkylamines with arylboronic acids in the absence of chemical oxidants. Couplings under these electrochemical conditions occur with higher yields and shorter reaction times than conventional reactions in air and provide complementary substrate reactivity.
- Walker, Benjamin R.,Manabe, Shuhei,Brusoe, Andrew T.,Sevov, Christo S.
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supporting information
p. 6257 - 6265
(2021/05/07)
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- Halogenated method of aromatic compound
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The invention belongs to the field of organic synthesis, and particularly relates to synthesis of aromatic halogens, in particular to arylamine. The invention discloses a synthesis method of a corresponding ortho-halogenated product from aromatic compounds such as carbazole and phenol. The method comprises the following steps: adding a metal sulfonate salt catalyst, aromatic amine, carbazole, phenol and other hydrogen - heteroatom-containing aromatic compound reaction substrates, a halogenation reagent and a reaction solvent at a specific reaction temperature. After the drying agent is dried, the yield of the reaction product and the nuclear magnetic characterization determining structure are determined by column chromatography. The reaction product yield is determined by gas chromatography. By adopting the method, under the cheap metal salt catalyst, a plurality of ortho-substituted brominated and chloro products can be obtained with moderate to excellent yield.
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Paragraph 0070-0073
(2021/11/10)
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- Reductive C?N Coupling of Nitroarenes: Heterogenization of MoO3 Catalyst by Confinement in Silica
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The construction of C?N bonds with nitroaromatics and boronic acids using highly efficient and recyclable catalysts remains a challenge. In this study, nanoporous MoO3 confined in silica serves as an efficient heterogeneous catalyst for C?N cross-coupling of nitroaromatics with aryl or alkyl boronic acids to deliver N-arylamines and with desirable multiple reusability. Experimental results suggest that silica not only heterogenizes the Mo species in the confined mesoporous microenvironment but also significantly reduces the reaction induction period and regulates the chemical efficiency of the targeted product. The well-shaped MoO3@m?SiO2 catalyst exhibits improved catalytic performance both in yield and turnover number, in contrast with homogeneous Mo catalysts, commercial Pd/C, or MoO3 nanoparticles. This approach offers a new avenue for the heterogeneous catalytic synthesis of valuable bioactive molecules.
- Yang, Fu,Dong, Xuexue,Shen, Yang,Liu, Mengting,Zhou, Hu,Wang, Xuyu,Li, Lulu,Yuan, Aihua,Song, Heng
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p. 3413 - 3421
(2021/07/31)
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- Electrochemical Reductive Arylation of Nitroarenes with Arylboronic Acids
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The synthesis of diarylamine is extremely important in organic chemistry. Herein, a novel electrochemical reductive arylation of nitroarenes with arylboronic acids was developed. A variety of diarylamines were synthesized without the need for transition-metal catalysts. The reaction could be scaled up efficiently in a flow cell and several derivatization reactions were carried out smoothly. Cyclic voltammetry experiments and mechanism studies showed that acetonitrile, formic acid, and triethyl phosphite all played a role in promoting this reductive arylation transformation.
- Wang, Dan,Wan, Zhaohua,Zhang, Heng,Alhumade, Hesham,Yi, Hong,Lei, Aiwen
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p. 5399 - 5404
(2021/10/20)
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- Synthesis and Characterization of a Tetradentate, N-Heterocyclic Carbene Copper(II) Complex and Its Use as a Chan-Evans-Lam Coupling Catalyst
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Copper N-heterocyclic carbenes (NHCs) are an emerging area of focus for catalysis and other applications. Using a straightforward methodology, a new and highly modifiable tetradentate copper(II) NHC complex was generated and characterized using X-ray crystallography, UV-vis and EPR spectroscopy, cyclic voltammetry, and ESI-MS. This copper(II) NHC complex adopted a distorted 4-coordinate coordination mode and demonstrates a unique absorption spectrum for a copper(II) species, but more interestingly, its redox properties indicate that it can readily access all three common copper oxidation states under atmospheric conditions. The tetradentate copper(II) NHC complex was used to catalytically generate new C-N bonds from a series of phenylboronic acids and amines. Once this CEL methodology was refined, moderate to high yields were achieved using catalytic amounts of the copper(II) complex to couple phenylboronic acids to a series of aniline derivatives. Substituted phenylboronic acids and anilines had minimal impact on the catalytic capabilities of this copper complex; however, there is some indication that steric interactions between catalyst and substrates may have an impact on efficient catalysis. The straightforward synthesis of this framework and the utilization of an inexpensive, first-row transition metal center in this system highlight the usefulness of copper(II) NHCs as catalyst for cross-coupling reactions.
- Cope, James D.,Sheridan, Patrick E.,Galloway, Christopher J.,Awoyemi, Raymond Femi,Stokes, Sean L.,Emerson, Joseph P.
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p. 4457 - 4464
(2021/01/09)
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- Copper complexes of 1,4-diazabutadiene ligands: Tuning of metal oxidation state and, application in catalytic C-C and C-N bond formation
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Reaction of 1,4-diazabutadiene (p-RC6H4N = C(H)(H)C = NC6H4R-p; R = OCH3, CH3, H and Cl; abbreviated as L-R) with CuCl2·2H2O in methanol at ambient temperature (25 °C) affords a group of doubly chloro-bridged dicopper complexes of type [{CuI(L-R)Cl}2], designated as 1-R. Similar reaction carried out in acetonitrile furnishes a family of doubly chloro-bridged dicopper complexes of type [{CuII(L-R)Cl2}2], designated as 2-R. Molecular structures of 1-OCH3 and 2-OCH3 have been determined by X-ray crystallography. While copper(I) is having a nearly tetrahedral N2Cl2 coordination sphere in 1-OCH3, the N2Cl3 coordination sphere around copper(II) is distorted square pyramidal in nature in 2-OCH3. Isolated 2-R complexes, on dissolution in methanol, are found to undergo facile reduction of the metal center to generate the corresponding 1-R complexes. The 1-R and 2-R complexes show intense absorptions in the visible and ultraviolet regions. Cyclic voltammetry on the 1-R and 2-R complexes shows both metal-centered and ligand centered redox responses. The 1-R complexes are found to efficiently catalyze C-N cross-coupling reactions between arylboronic acids and aryl amines; while the 2-R complexes display notable catalytic efficiency for nitroaldol reactions.
- Mukherjee, Aparajita,Basu, Semanti,Bhattacharya, Samaresh
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- Chan-Evans-Lam C?N Coupling Promoted by a Dinuclear Positively Charged Cu(II) Complex. Catalytic Performance and Some Evidence for the Mechanism of CEL Reaction Obviating Cu(III)/Cu(I) Catalytic Cycle
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In the present study, we report the synthesis of a series of copper(II) complexes with a wide range of ligands and their testing in the copper catalyzed Chan-Evans-Lam (CEL) coupling of aniline and phenylboronic acid. The efficiency of the coupling was directly connected with the ease of the reduction of Cu(II) to Cu(I) of the complexes. The most efficient catalyst was derived from 4-t-butyl-2,5-bis[(quinolinylimino)methyl]phenolate and two Cu(II) ions. Depending on the counter-anion nature and the concentration of the reaction mixture, the reaction can be directed to predominant C?N-bond formation. Forty-three derivatives of diphenylamine were prepared under the optimized conditions. The proposed mechanism of the catalysis was based on the reduction potential of a series of complexes, molecular weight measurements of the catalytic complex in MeOH and the kinetic studies of aniline and phenylboronic acid coupling. In addition, an 1H NMR experiment in a sealed NMR tube, without external oxygen supply available, proved that no complete Cu(II) to Cu(I) conversion was observed under the condition, ruling out the usually accepted mechanism of the C?N coupling, which included the oxygenation of the intermediately formed Cu(I) complexes after the key step of C?N conversion had already been completed. Instead, a mechanism was proposed, involving an oxygen molecule coordinated to two copper ions in the key C?N bond formation without any detectable conversion of the Cu(II) complexes to Cu(I).
- Akatyev, Nikolay,Il'in, Mikhail,Il'in, Mikhail,Peregudova, Svetlana,Peregudov, Alexander,Buyanovskaya, Anastasiya,Kudryavtsev, Kirill,Dubovik, Alexander,Grinberg, Valerij,Orlov, Victor,Pavlov, Alexander,Novikov, Valentin,Volkov, Ilya,Belokon, Yuri
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p. 3010 - 3021
(2020/04/29)
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- PROSTACYCLIN RECEPTOR AGONIST
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A compound represented by formula (I) or an isomer or a pharmaceutically acceptable salt thereof. The present invention also relates to an application of the same in preparing a drug for treating a disease related to a PGI2 receptor.
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Paragraph 0088-0090
(2020/12/22)
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- Imidazole-directed fabrication of three polyoxovanadate-based copper frameworks as efficient catalysts for constructing C-N bonds
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A synthetic pathway for the directed preparation of three novel polyoxovanadate-based copper frameworks (POVCFs), i.e., [Cu0.5(1-ipIM)2]2[V4O11] (POVCF 1), [Cu(1-ipIM)2](VO3)2 (POVCF 2) and [Cu(1-pIM)4](HpIM)4[V10O28] (POVCF 3) (1-ipIM = 1-isopropylimidazole; 1-pIM = 1-propylimidazole) using bifunctional imidazole molecules as organic ligands and base has been developed. Systematic studies revealed that the variable base enviroment in the reaction is the key step in the preparation of 1D to 3D supermolecular networks of POVCFs 1-3. Single crystal X-ray diffraction analyses demonstrated that the Cu2+ atoms of POVCFs 1-2 were coordinated with four imidazole derivative molecules and two different polyoxovanadate {[V4O11]2- and [V10O28]6-} clusters, respectively, exhibiting a [CuN4O2] binding set and a distorted octahedral geometry. Specifically, POVCF 1 exhibited adjacent [V4O11]2- that dangle up and down arranged in a parallel 2D network and further coordinated with [Cu(1-ipIM)4]2+ to form a 3D supramolecular structure. However, POVCF 3 presented one tetrahedral coordinated vanadium atom and one four-coordinated copper atom and they further gave rise to a 1D network by the Cu-O and V-O bonds. More importantly, these POVCFs were further studied in the construction of C-N bond reactions of primary amines under mild conditions, and it was found that POVCF 1 displayed efficient heterogeneous catalytic activities in the Chan-Lam reaction (yields up to 89%). This journal is
- Gong, Shuwen,Gu, Yuxiao,Huang, Xianqiang,Li, Jikun,Li, Qiang,Qi, Yuquan,Shen, Guodong
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p. 10970 - 10976
(2020/09/02)
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- Continuous Synthesis of Aryl Amines from Phenols Utilizing Integrated Packed-Bed Flow Systems
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Aryl amines are important pharmaceutical intermediates among other numerous applications. Herein, an environmentally benign route and novel approach to aryl amine synthesis using dehydrative amination of phenols with amines and styrene under continuous-flow conditions was developed. Inexpensive and readily available phenols were efficiently converted into the corresponding aryl amines, with small amounts of easily removable co-products (i.e., H2O and alkanes), in multistep continuous-flow reactors in the presence of heterogeneous Pd catalysts. The high product selectivity and functional-group tolerance of this method allowed aryl amines with diverse functional groups to be selectively obtained in high yields over a continuous operation time of one week.
- Ichitsuka, Tomohiro,Kobayashi, Shū,Koumura, Nagatoshi,Sato, Kazuhiko,Takahashi, Ikko
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p. 15891 - 15896
(2020/07/13)
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- Copper(I)–creatine complex on magnetic nanoparticles as a green catalyst for N- and O-arylation in deep eutectic solvent
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Immobilization of copper(I) ions on magnetic nanoparticles was performed using surface modification of Fe3O4 with creatine. Fe3O4?creatine-Cu(I) magnetic catalyst was synthesized and applied in C&bond;X cross-coupling reactions with aryl halides in a deep eutectic as a green solvent. The results indicate the Fe3O4?creatine-Cu(I) magnetic nanoparticles showed excellent activity and high stability. In addition, it was revealed that this catalyst can be recycled five times without significant loss in catalytic activity.
- Bagheri, Sepideh,Heydari, Akbar,Pazoki, Farzane,Radfar, Iman
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- Diaza crown-type macromocycle (kryptofix 22) functionalised carbon nanotube for efficient Ni2+ loading; A unique catalyst for cross-coupling reactions
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Raising the capability of supporting and suppressing the leaching possibility to a very insignificant level has still remained challenging for some class of transition metals, i.e. Ni2+. Here we present the covalent functionalisation of macrocyclic ligand, 4,13-diaza-18-crown-6 (kryptofix 22), on the surface of carbon nanotube (CNT), leading to a unique adsorptive capability for supporting Ni2+. This material was incorporated as a promising catalyst in coupling reactions including C[sbnd]C, CN, and CO[sbnd][sbnd] cross-coupling reactions. We demonstrate that the kryptofix 22 functionalisation on the surface of CNT has a key role in the enhancement of the adsorption capability Ni2+ and subsequent catalytic activity. We further prove that this ligand causes a significant boost in the recyclability of the reactions due to the extremely trivial Ni2+ leaching from the CNT's surface during the reactions.
- Aalinejad, Michael,Doustkhah, Esmail,Pesyan, Nader Noroozi
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- Electrochemically Enabled Chan-Lam Couplings of Aryl Boronic Acids and Anilines
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The Chan-Lam reaction remains a highly utilized transformation for C-N bond formation. However, anilines remain problematic substrates due to their lower nucleophilicity. To address this problem, we developed an electrochemically mediated Chan-Lam coupling of aryl boronic acids and amines utilizing a dual copper anode/cathode system. The mild conditions identified have enabled the preparation of a wide range of functionalized biarylanilines in good yields and chemoselectivities.
- Wexler, Ryan P.,Nuhant, Philippe,Senter, Timothy J.,Gale-Day, Zachary J.
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supporting information
p. 4540 - 4543
(2019/06/27)
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- “On Water” promoted N-arylation reactions using Cu (0)/myo-inositol catalytic system
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Myo-inositol is originally applied as a cardiovascular medicine in clinic, which can be multi-ton manufactured via extraction from the byproducts in agricultural product processing such as defatted rice bran and corn-soaking water. Herein, the application of myo-inositol (MI) as a novel versatile tridentate O-donor ligand has been first described for promoting Cu-catalyzed amination reaction in aqueous medium.
- Zhou, Qifan,Du, Fangyu,Chen, Yuanguang,Fu, Yang,Chen, Guoliang
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supporting information
p. 1938 - 1941
(2019/06/24)
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- CoII immobilized on an aminated magnetic metal-organic framework catalyzed C-N and C-S bond forming reactions: A journey for the mild and efficient synthesis of arylamines and arylsulfides
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In this work, we report a simple and versatile method for the modification of a metal-organic framework (NH2-MIL53(Al)) in a step-wise manner. To characterize the synthesized nanostructured catalyst, a variety of spectroscopic and microscopic techniques including FT-IR, XRD, BET, TEM, FE-SEM, EDX, EDX-mapping, TGA, XPS, VSM, ICP-OES and CHN have been employed. Fe3O4@AMCA-MIL53(Al)-NH2-CoII NPs, which benefit from small nanocrystalline size (10-30 nm, according to the XRD and TEM data) in combination with the coexistence of magnetic nanoparticles, a metal-organic framework, and cobalt species, were found to be an excellent environment catalyst to promote the C-N and C-S cross coupling reactions. A wide range of functional substrates including electron-withdrawing and electron-donating aryl halides underwent the coupling reaction with aromatic/heteroaromatic/benzylic and aliphatic amines and sulfides. The results demonstrated that the yields of the target products were good to excellent and the catalyst can be recycled for at least seven recycling runs without a discernible decrease in its catalytic activity. Furthermore, the heterogeneity studies (such as hot filtration and poisoning tests) efficiently confirmed that the as-synthesized nanostructured catalyst is heterogeneous and completely stable under the reaction conditions. We hope that our study inspires more interest in designing novel catalysts based on using low-cost metal ions (such as cobalt) in the field of cross coupling reactions.
- Mohammadinezhad, Arezou,Akhlaghinia, Batool
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supporting information
p. 15525 - 15538
(2019/10/19)
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- Recyclable bimetallic CuMoO4 nanoparticles for C-N cross-coupling reaction under mild conditions
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Herein we disclosed inexpensive copper(ii) bimetallic CuMoO4 nanoparticles for the C-N cross-coupling reaction of alkyl and aryl amines with haloarenes. The reaction proceeds under mild and ligand free conditions. The catalyst is recyclable and effective for a wide range of amines and haloarenes. Here, the efficiency of the Cu(ii) catalyst is increased by doping molybdenum metal. The bimetallic nanoparticles are anticipated to proceed via normal oxidative addition and reductive eliminations.
- Panigrahi, Reba,Panda, Subhalaxmi,Behera, Pradyota Kumar,Sahu, Santosh Kumar,Rout, Laxmidhar
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supporting information
p. 19274 - 19278
(2019/12/24)
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- Preparation and characterization of isatin complexed with Cu supported on 4-(aminomethyl) benzoic acid-functionalized Fe3O4 nanoparticles as a novel magnetic catalyst for the Ullmann coupling reaction
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Isatin complexed with Cu supported on 4-(aminomethyl) benzoic acid-functionalized Fe3O4 nanoparticles (Cu-IS-AMBA-MNPs) as a new catalyst was designed, prepared and characterized by appropriate analyses. The heterogeneous reusable catalyst was successfully used for the efficient and widespread syntheses of diaryl ethers and diarylamines via the Ullmann coupling reaction. This green catalyst was easily removed, reused several times with no significant loss of its activity, and provided a clean synthesis with excellent yield and reduced time.
- Khodaei, Mohammad Mehdi,Alizadeh, Abdolhamid,Haghipour, Maryam
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p. 2727 - 2747
(2019/02/13)
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- Copper-catalyzed, ceric ammonium nitrate mediated N-arylation of amines
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Cu-Catalyzed, ligand- and base-free cross-coupling of aryl boronic acids with primary and secondary amines has been reported. This ‘Chan-Evans-Lam' reaction has revealed that at room temperature, with a catalytic amount of copper(ii) acetate and ceric ammonium nitrate (CAN) as an oxidant, N-arylation can result in an effective C-N bond formation. This air stable, practical, robust protocol enables tolerance towards a variety of functional groups on both boronic acid and amine partners.
- Gonela, Uma Maheshwar,Ablordeppey, Seth Y.
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supporting information
p. 2861 - 2864
(2019/02/17)
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- INHIBITORS OF PLATELET FUNCTION AND METHODS FOR USE OF THE SAME
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Disclosed herein are small molecule inhibitors of platelet function, and methods of using the small molecules to treat diseases, such as platelet hemostasis and thrombosis. In particular, disclosed herein are compounds of Formula (I) and pharmaceutically acceptable salts thereof: wherein the substituents are as described.
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Paragraph 0070
(2019/11/12)
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- Ullmann-type: N-arylation of anilines with alkyl(aryl)sulfonium salts
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A palladium/copper-cocatalyzed Ullmann-type N-arylation of anilines using alkyl(aryl)sulfonium triflates as arylation reagents has been accomplished. The reaction enabled Caryl-S bond cleavage over Calkyl-S bond breakage of alkyl(aryl)sulfoniums by Pd(P(tBu)3)2/CuI and gave the corresponding N-arylated products in good to high yields. It was also significant that the reactions of aniline with asymmetric butyl(mesityl)(aryl)sulfonium triflates showed excellent selectivity, in which the aryl groups other than the bulky and electron-rich mesityl moieties were transformed.
- Tian, Ze-Yu,Zhang, Cheng-Pan
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p. 11936 - 11939
(2019/10/11)
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- Copper-Catalyzed NaBAr 4-Based N-Arylation of Amines
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Using NaBAr 4 as an arylating agent, the formation of carbon-heteroatom bonds by a Cham-Lam cross-coupling reaction in the presence of catalytic copper(II) acetate monohydrate in acetonitrile at room temperature under air is described. The investigation of reaction scope suggests that several aliphatic and aromatic amines are compatible. In particular, the reaction of alkylamine and NaBAr 4 proceeds smoothly to offer the corresponding products in good to excellent yields.
- Yang, Qin,Lei, Xiaoli,Yin, Zhijian,Deng, Zhihong,Peng, Yiyuan
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supporting information
p. 538 - 544
(2019/01/10)
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- Reductive Molybdenum-Catalyzed Direct Amination of Boronic Acids with Nitro Compounds
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The synthesis of aromatic amines is of utmost importance in a wide range of chemical contexts. We report a direct amination of boronic acids with nitro compounds to yield (hetero)aryl amines. The novel combination of a dioxomolybdenum(VI) catalyst and triphenylphosphine as inexpensive reductant has revealed to be decisive to achieve this new C?N coupling. Our methodology has proven to be scalable, air and moisture tolerant, highly chemoselective and engages both aliphatic and aromatic nitro compounds. Moreover, this general and step-economical synthesis of aromatic secondary amines showcases orthogonality to other aromatic amine syntheses as it tolerates aryl halides and carbonyl compounds.
- Suárez-Pantiga, Samuel,Hernández-Ruiz, Raquel,Virumbrales, Cintia,Pedrosa, María R.,Sanz, Roberto
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supporting information
p. 2129 - 2133
(2019/01/25)
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- Peptide Nanofiber Templated Zinc Oxide Nanostructures as Non-precious Metal Catalyzed N-Arylation of Amines, One-Pot Synthesis of ImidazoHeterocycles and Fused Quinazolines
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In the present study, peptide nanofiber was used to immobilize zinc oxide. This nanoparticle was prepared through self-assembly in an aqueous solution. The structural properties of the prepared catalyst were examined by a series of techniques, such as FT-IR, EDS, SEM, TEM, XRD, ICP-OES (inductively coupled plasma optical emission spectrometry), and ultraviolet–visible (UV–Vis) spectroscopy. TEM images showed the necklace model for peptide nanofiber decorated with zinc oxide. The versatility of the method was investigated by N-arylation using reaction of amines with hydroxybenzotriazole as a novel phenylating reagent, one-pot synthesis of imidazoheterocycles by a three-component reaction of 2-aminopyridine, aldehyde, terminal alkyne and preparation of tetracyclic quinazolinone ring by one-pot reaction of isatoic anhydride, amine, and ninhydrin. High yields, low cost of catalyst, environmental friendliness, efficient recovery and recyclability of catalyst are the most important features of this catalytic system.
- Taherinia, Zahra,Ghorbani-Choghamarani, Arash,Hajjami, Maryam
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p. 151 - 168
(2018/10/26)
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- Copper immobilized at a covalent organic framework: An efficient and recyclable heterogeneous catalyst for the Chan-Lam coupling reaction of aryl boronic acids and amines
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A polyimide covalent organic framework (PI-COF) with high thermal and chemical stabilities has been readily prepared from commercially available and inexpensive reagents and was employed as an effective support for heterogeneous copper. It was demonstrated that the obtained Cu@PI-COF is a highly active heterogeneous catalyst which can effectively promote the Chan-Lam coupling reaction of aryl boronic acids and amines in an open flask without the aid of any base or additive. In addition, the catalyst could be readily recovered from the reaction mixture by simple filtration and reused for at least eight cycles without any observable change in structure and catalytic activity.
- Han, Yi,Zhang, Mo,Zhang, Ya-Qing,Zhang, Zhan-Hui
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p. 4891 - 4900
(2018/11/21)
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- CuCl heterogenized on metformine-modified multi walled carbon nanotubes as a recyclable nanocatalyst for Ullmann-type C-O and C-N coupling reactions
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Herein, a novel MWCNTs-Met/CuCl nanocatalyst synthesis method by metformine covalent grafting on the surface of carbon nanotubes and subsequent coordination with a CuCl catalyst is described. The nanocatalyst formation was analyzed by FTIR, energy dispersive spectroscopy (EDS), Raman spectroscopy and ICP analysis. The nanocatalyst morphology was examined by transmission and scanning electron microscopies (TEM and SEM). Moreover, in the N-arylation of anilines and indole, the nanocatalyst (MWCNTs-Met/CuCl) could be successfully used by formation of intermolecular C(aryl)-N bonds of the relevant aryl halides (Ar-I, Ar-Br, Ar-Cl) with amines by coupling reactions of Ullmann-type. The O-arylation of substituted phenols is also promoted by this heterogeneous copper catalyst with different aryl iodides and bromides. Additionally, without any considerable loss in activity, the novel catalyst was recovered and recycled several times.
- Akhavan, Elham,Hemmati, Saba,Hekmati, Malak,Veisi, Hojat
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p. 2782 - 2789
(2018/02/19)
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- Metal-free synthesis of secondary amines by the reaction of tosyl triazene and aryl boronic acid
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A metal free noncatalytic amination process has been developed for the synthesis of N-substituted aniline using a new amine source. The amine source p-toluene sulfonyl triazene (PhN?NNHTs) has been prepared by treating aryldiazonium salt with p-tosylamide. Various unsymmetrical amines could be synthesized by treating this reagent and boronic acid in toluene at 110 °C in the presence of DBU and 4 ? molecular sieve. A large variety of N-substituted aniline could be synthesized with moderate yield.
- Sarma, Manas Jyoti,Phukan, Prodeep
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p. 656 - 662
(2018/02/19)
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- An Effective Heterogeneous Copper Catalyst System for C-N Coupling and Its Application in the Preparation of 2-Methyl-4-methoxydiphenylamine (MMDPA)
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A ligand-recyclable, environmentally benign heterogeneous catalyst system composed of CuI and polystyrene-supported N (-(4-(aminomethyl)naphthalen-1-yl)- N (-phenyl-1 H -pyrrole-2-carbohydrazide (PSAP) has been established for Ullmann type C-N coupling based on the homogeneous catalyst system N ′, N ′-diphenyl-1 H -pyrrole-2-carbohydrazide/CuI. This heterogeneous catalyst system maintained the catalytic effectiveness of the homogeneous catalyst. A variety of functionalized aryl bromides can be efficiently aminated with aryl amines and aliphatic amines with high selectivity for amines over alcohols. Moreover, a practical application of this catalyst system to promote the reaction of commercially available 4-methoxy-2-methylaniline and bromobenzene in 10 mmol scale, provided 2-methyl-4-methoxydiphenylamine (MMDPA) with 93% yield with the merit of the approach being simple operation for work-up and purification.
- Yi, Zhou,Huang, Manna,Wan, Yiqian,Zhu, Xinhai
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p. 3911 - 3920
(2018/09/29)
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- A new diphosphine-carbonyl complex of ruthenium: an efficient precursor for C-C and C-N bond coupling catalysis
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Reaction of 1,2-bis(diphenylphosphino)benzene (dppbz) with [{Ru(CO)2Cl2}n] affords [Ru(dppbz)(CO)2Cl2], where the two carbonyls are mutually cis and the two chlorides are trans. The molecular structure of [Ru(dppbz)(CO)2Cl2], has been determined by X-ray crystallography, and the stability of the different available stereoisomers has been computationally evaluated. [Ru(dppbz)(CO)2Cl2] has been found to serve as an excellent pre-catalyst for catalytic Suzuki-type C-C coupling and Buchwald-type C-N coupling reactions.
- Mukherjee, Aparajita,Hrovat, David A.,Richmond, Michael G.,Bhattacharya, Samaresh
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p. 10264 - 10272
(2018/08/06)
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- Nickel Dual Photoredox Catalysis for the Synthesis of Aryl Amines
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In this work, a new dual photoredox nickel catalysis system has been utilized for the synthesize of aryl amines. Previously, our group has shown that a nickel catalyst in conjunction with a photosensitizer and a sacrificial electron donor can cross-couple C-C bonds via photoredox-assisted reductive coupling. Here we have built upon that system to develop a redox-neutral cross-coupling system for the formation of C-N bonds. The catalytic system is composed of just a nickel cross-coupling catalyst, a Ru photocatalyst, and base and is capable of coupling amines with aryl halides in good to excellent yields. Furthermore, it was found that these reactions are functional under ambient conditions with catalyst loadings of 1 mol %. Spectroscopic studies provide support that this amination mechanism proceeds via a nitrogen-based radical intermediate. This N-radical mechanism offers direct synthetic access to di- and triaryl amines from nickel photocatalysis.
- Key, Ryan J.,Vannucci, Aaron K.
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p. 1468 - 1472
(2018/05/23)
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- Immobilization of nickel ions onto the magnetic nanocomposite based on cross-linked melamine groups: Effective heterogeneous catalyst for N-Arylation of Arylboronic acids
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A new magnetic heterogeneous catalyst was synthesized by immobilization of nickel ions onto a cross-linked polymeric nanocomposite composed of cyanuric chloride, ethylenediamine and functionalized magnetic nanoparticles. The resulting nitrogen rich support was capable of adsorbing large amounts of nickel ions (1.20 mmol g?1). The synthesized catalyst was characterized using AAS, TEM, FT-IR, EDX, TGA, SEM, BET and XRD techniques. The performance of the prepared catalyst was investigated in the C-N coupling of arylamines with aryl boronic acids. The reaction was carried out under a mild condition and good to moderate to good yields of products was obtained using only 5.0 mol% of the catalyst. The catalyst was easily recovered and reused for at least 7 times without any significant loss of its activity.
- Pourjavadi, Ali,Keshavarzi, Nahid,Moghaddam, Firouz Matloubi,Hosseini, Seyed Hassan
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- Intermolecular Reductive C-N Cross Coupling of Nitroarenes and Boronic Acids by PIII/PV=O Catalysis
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A main group-catalyzed method for the synthesis of aryl- and heteroarylamines by intermolecular C-N coupling is reported. The method employs a small-ring organophosphorus-based catalyst (1,2,2,3,4,4-hexamethylphosphetane) and a terminal hydrosilane reductant (phenylsilane) to drive reductive intermolecular coupling of nitro(hetero)arenes with boronic acids. Applications to the construction of both Csp2-N (from arylboronic acids) and Csp3-N bonds (from alkylboronic acids) are demonstrated; the reaction is stereospecific with respect to Csp3-N bond formation. The method constitutes a new route from readily available building blocks to valuable nitrogen-containing products with complementarity in both scope and chemoselectivity to existing catalytic C-N coupling methods.
- Nykaza, Trevor V.,Cooper, Julian C.,Li, Gen,Mahieu, Nolwenn,Ramirez, Antonio,Luzung, Michael R.,Radosevich, Alexander T.
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supporting information
p. 15200 - 15205
(2018/11/30)
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- Transition-metal-free synthesis of aromatic amines via the reaction of benzynes with isocyanates
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An unexpected reaction between benzynes and isocyanates to generate aromatic amines has been developed under transition-metal-free conditions. The in situ prepared anions formed through cleavage of the N–C bond in isocyanates, reacted with aryne precursor
- Seo, Jeong Hoon,Ko, Haye Min
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supporting information
p. 671 - 674
(2018/01/19)
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- Transition-Metal-Free N-Arylation of Amines by Triarylsulfonium Triflates
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A simple and efficient method for transition-metal-free N-arylation of various amines by triarylsulfonium triflates is described. Both aliphatic and aromatic amines were smoothly converted at 80 °C in the presence of tBuOK or KOH to give the corresponding mono N-arylated products in good to high yields. The molar ratios of the reactants and the choice of bases had a big effect on the reaction. When a large excess of [Ph3S][OTf] and tBuOK were employed for primary amines under the standard conditions, the bis(N-phenyl) products were predominantly formed. This method was also applicable to the synthesis of bioactive N-phenyl amino acid derivatives. The control experiments, the deuterium labelling study, and the presence of regioisomers of N-arylated products when using 4-substituted triarylsulfonium triflates suggested that the reaction might proceed through an aryne intermediate. The present protocol demonstrated that triarylsulfonium salts are versatile arylation reagents in the construction of CAr?N bonds.
- Tian, Ze-Yu,Ming, Xiao-Xia,Teng, Han-Bing,Hu, Yu-Tian,Zhang, Cheng-Pan
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p. 13744 - 13748
(2018/09/14)
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- Palladium-catalyzed amination of aryl sulfoxides
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Amination of diaryl sulfoxides with anilines and alkylamines has been accomplished under palladium/N-heterocyclic carbene (NHC) catalysis. Owing to its electron deficiency, the leaving arenesulfenate anion would be smoothly released from the palladium center to result in uneventful catalyst turnover under milder reaction conditions in comparison with previous C-S bond amination reactions. This amination accommodated a wider range of functional groups such as silyl, boryl, methylsulfanyl, and halogen moieties. Regioselective amination of unsymmetrical diaryl sulfoxides was also executed by means of steric bias.
- Yoshida, Yuto,Otsuka, Shinya,Nogi, Keisuke,Yorimitsu, Hideki
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supporting information
p. 1134 - 1137
(2018/02/23)
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- Synthesis and characterization of MCM-41-Biurea-Pd as a heterogeneous nanocatalyst and using its catalytic efficacy in C–C, C–N and C–O coupling reactions
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MCM-41-Biurea-Pd is introduced as a new, heterogeneous and reusable catalyst for C–C and C–heteroatom bond formation between various aryl halides, phenols and amines, in the presence of Ph3SnCl (Stille reaction) in PEG-400 as a green solvent at room temperature. The structure of the functionalized MCM-41 was analysed using various techniques.
- Batmani, Hana,Noroozi Pesyan, Nader,Havasi, Forugh
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- The invention relates to a N, N - disubstituted hydrazide as ligand copper catalysis C - N coupling method (by machine translation)
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The invention discloses a to N, N - disubstituted hydrazide as ligand copper catalysis C - N coupling method, the method uses the aromatic halides with amine compound as a raw material, in order to alcohol compound as the solvent, in order to copper or copper compound as a catalyst, in order to as formula I or formula II as shown by a N, N - disubstituted hydrazide as a ligand, the presence of a base, in the 10 - 130 °C generating C - N coupled reaction for generating N - aryl compound: the invention mild reaction conditions, high chemical selectivity, substrate and wide range of application, simplicity of operation, product is simple and easy to separation and environmental protection, the obtained product yield is higher. Wherein R1, R2 is selected from methyl, phenyl, 4 - methoxyphenyl, 4 - nitro-phenyl, 2 - methylphenyl, 2 - isopropyl phenyl; R3 is hydrogen or methoxy. (by machine translation)
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Paragraph 0121-0123
(2017/07/21)
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- Room-Temperature CuI-Catalyzed Amination of Aryl Iodides and Aryl Bromides
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A general and effective CuI/N′,N′-diaryl-1H-pyrrole-2-carbohydrazide catalyst system was developed for the amination of aryl iodides and bromides at room temperature with good chemoselectivity between -OH and -NH2 groups. Only 5 mol % of CuI and ligands was needed in this protocol to effect the amination of various aryl bromides and aryl iodides with a wide range of aliphatic and aryl amines (1.3 equiv).
- Ding, Xiaomei,Huang, Manna,Yi, Zhou,Du, Dongchen,Zhu, Xinhai,Wan, Yiqian
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p. 5416 - 5423
(2017/05/25)
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- High Catalytic Activity of Peptide Nanofibres Decorated with Ni and Cu Nanoparticles for the Synthesis of 5-Substituted 1H-Tetrazoles and N-Arylation of Amines
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A rapid development of a new methodology for decarboxylative N-arylation of carboxylic acids and the preparation of 5-substituted 1H-tetrazoles catalysed by peptide nanofibres decorated with Cu and Ni nanoparticles is presented. Compared with conventional aryl halides, benzoic acids are extremely interesting and environmentally friendly options for the synthesis of secondary aryl amines.
- Ghorbani-Choghamarani, Arash,Taherinia, Zahra
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p. 1127 - 1137
(2017/10/10)
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- The solid copper-mediated C-N cross-coupling of phenylboronic acids under continuous flow conditions
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We have developed two general methods for the C-N cross-coupling of phenylboronic acids with amines using solid copper flow reactors, in combination with an oxidant. We have developed one method for a C-N arylation reaction which employs a solid copper coil reactor, in combination with tert-butyl peroxybenzoate, to give products in moderate isolated yields. We have also developed a general method for the C-N cross coupling of phenylboronic acids using a column packed with solid copper powder, in combination with acetic acid and TEMPO, to give products in isolated yields in excess of 75+%. We have also applied our general copper powder method to generate a library of products which highlights the utility of solid copper flow reactors for C-N cross coupling reactions, generating 16 examples in good yields. Mechanistic implications and future directions are also discussed.
- Bao, Jennifer,Tranmer, Geoffrey K.
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p. 654 - 657
(2016/01/26)
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- Highly Chemoselective Iridium Photoredox and Nickel Catalysis for the Cross-Coupling of Primary Aryl Amines with Aryl Halides
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A visible-light-promoted iridium photoredox and nickel dual-catalyzed cross-coupling procedure for the formation C?N bonds has been developed. With this method, various aryl amines were chemoselectively cross-coupled with electronically and sterically diverse aryl iodides and bromides to forge the corresponding C?N bonds, which are of high interest to the pharmaceutical industries. Aryl iodides were found to be a more efficient electrophilic coupling partner. The coupling reactions were carried out at room temperature without the rigorous exclusion of molecular oxygen, thus making this newly developed Ir-photoredox/Ni dual-catalyzed procedure very mild and operationally simple.
- Oderinde, Martins S.,Jones, Natalie H.,Juneau, Antoine,Frenette, Mathieu,Aquila, Brian,Tentarelli, Sharon,Robbins, Daniel W.,Johannes, Jeffrey W.
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supporting information
p. 13219 - 13223
(2016/10/30)
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- Nitro resin supported copper nanoparticles: An effective heterogeneous catalyst for [Formula presented] cross coupling and oxidative [Formula presented] homocoupling
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In the present study, we investigate the synthesis and catalytic activity of copper nanoparticles (CuNPs) stabilized onto a novel nitro functionalized polystyrene resin. The deposited nanoparticles were characterized by various analytical techniques and TEM images, revealed uniformly distributed copper nanoparticles of sizes 3–9?nm. We effectively used the resin impregnated CuNPs for [Formula presented] coupling of various aromatic amines with aryl halides and for the oxidative [Formula presented] homocoupling of phenyacetylene. Further, recycling of the catalyst, leaching of metal ions and post reaction changes in the support were studied and it was concluded that the support acts as oxidant during the homocoupling of phenyl acetylene which is oxidative by nature.
- Barot, Nirav,Patel, Sunil B.,Kaur, Harjinder
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- A quick Chan-Lam C-N and C-S cross coupling at room temperature in the presence of square pyramidal [Cu(DMAP)4I]I as a catalyst
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A rapid and efficient protocol for C-N and C-S cross coupling has been developed using a new square pyramidal copper complex, [Cu(DMAP)4I]I. The complex was successfully synthesized via a disproportionation reaction of CuI and DMAP in DMSO. The catalytic activity of the complex was found to be excellent for Chan-Lam coupling reaction between aryl boronic acid and amine, amide, azide or thiol. The reaction could be carried out in the presence of only 2 mol% of the copper catalyst in methanol at room temperature within a short time.
- Roy, Subhasish,Sarma, Manas Jyoti,Kashyap, Bishwapran,Phukan, Prodeep
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supporting information
p. 1170 - 1173
(2016/01/15)
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