- Cu-ACP-Am-Fe3O4@SiO2: an efficient and recyclable heterogeneous catalyst for the Chan–Lam coupling reaction of boronic acids and amines
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Abstract: We have developed an efficient method for Cu-ACP-Am-Fe3O4@SiO2 catalyzed Chan–Lam coupling of phenylboronic acid with primary amine furnished secondary amines. The catalyst offered virtues like mild reaction conditions, magnetically separable, and reusable and exhibits excellent performance in terms of good product yield and high turnover number. Graphic abstract: [Figure not available: see fulltext.]
- Vibhute, Sandip P.,Mhaldar, Pradeep M.,Gaikwad, Dipak S.,Shejwal, Rajendra V.,Pore, Dattaprasad M.
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- In Situ Formation of Cationic π-Allylpalladium Precatalysts in Alcoholic Solvents: Application to C-N Bond Formation
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We report an efficient Buchwald-Hartwig cross-coupling reaction in alcoholic solvent, in which a low catalyst loading showed excellent performance for coupling aryl halides (I, Br, and Cl) with a broad set of amines, amides, ureas, and carbamates under mild conditions. Mechanistically speaking, in a protic and polar medium, extremely bulky biarylphosphine ligands interact with the dimeric precatalyst [Pd(π-(R)-allyl)Cl]2 to form the corresponding cationic complexes [Pd(π-(R)-allyl)(L)]Cl in situ and spontaneously. The resulting precatalyst further evolves under basic conditions into the corresponding L-Pd(0) catalyst, which is commonly employed for cross-coupling reactions. This mechanistic study highlights the prominent role of alcoholic solvents for the formation of the active catalyst.
- Bailly, Aurélien,Bihel, Frédéric,Grimaud, Laurence,Oliva, Estefania,Schmitt, Martine,Steinsoultz, Philippe,Wagner, Patrick
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p. 560 - 567
(2022/01/03)
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- (DiMeIHeptCl)Pd: A Low-Load Catalyst for Solvent-Free (Melt) Amination
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(DiMeIHeptCl)Pd, a hyper-branched N-aryl Pd NHC catalyst, has been shown to be efficient at performing amine arylation reactions in solvent-free ("melt") conditions. The highly lipophilic environment of the alkyl chains flanking the Pd center serves as lubricant to allow the complex to navigate through the paste-like environment of these mixtures. The protocol can be used on a multi-gram scale to make a variety of aniline derivatives, including substrates containing alcohol moieties.
- Semeniuchenko, Volodymyr,Sharif, Sepideh,Day, Jonathan,Chandrasoma, Nalin,Pietro, William J.,Manthorpe, Jeffrey,Braje, Wilfried M.,Organ, Michael G.
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p. 10343 - 10359
(2021/07/31)
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- Nickel-Catalyzed Amination of Aryl Nitriles for Accessing Diarylamines through C?CN Bond Activation
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A nickel-catalyzed amination to access diarylamines has been developed through C?CN bond activation of aryl nitriles with anilines. In this developed catalytic protocol, various aromatic and heteroaromatic nitriles could be utilized as the electrophiles to couple with substituted anilines. A diversity of diarylamines were obtained in 15–95% yields. (Figure presented.).
- Wu, Ke,Rong, Qiang,Sun, Nan,Hu, Baoxiang,Shen, Zhenlu,Jin, Liqun,Hu, Xinquan
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p. 4708 - 4713
(2021/08/27)
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- Design, preparation and characterization of aerogel NiO-CuO-CoO/SiO2 nanocomposite as a reusable catalyst for C-N cross-coupling reaction
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Aerogels are porous, non-crystalline solid materials with high specific surface space, plentiful three-dimensional (3D) porous construction, ultra-low density and significant porosity. The aerogel nanocomposite is produced using sol-gel and supercritical drying processes. CO2 supercritical drying (SCD) is the most powerful process, ensuring optimal product properties such as high porosity, low density, and high thermal conductivity. On this account, we used the CO2 supercritical drying method to produce NiO-CuO-CoO/SiO2 nanocomposite aerogels and applied it as a reusable catalyst for the C-N cross-coupling reaction (Buchwald-Hartwig amination). Powerful catalytic activity for the C-N cross-coupling reaction was obtained for the new nanocomposite aerogel, that is, NiO-CuO-CoO/SiO2. The catalyst was characterized by X-ray Powder Diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), elemental mapping and Brunauer-Emmett-Teller (BET). Also, organic compounds were identified by melting point, Fourier-transform infrared spectroscopy (FT-IR) and hydrogen-1 nuclear magnetic resonance (1H NMR) analyses.
- Ghasemi, Amir Hossein,Naeimi, Hossein
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supporting information
p. 5056 - 5063
(2020/04/09)
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- Nickel-Catalyzed Amination of Aryl Thioethers: A Combined Synthetic and Mechanistic Study
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Herein, we report a nickel-1,2-bis(dicyclohexylphosphino)ethane (dcype) complex for the catalytic Buchwald-Hartwig amination of aryl thioethers. The protocol shows broad applicability with a variety of different functional groups tolerated under the catalytic conditions. Extensive organometallic and kinetic studies support a nickel(0)-nickel(II) pathway for this transformation and revealed the oxidative addition complex as the resting state of the catalytic cycle. All the isolated intermediates have proven to be catalytically and kinetically competent catalysts for this transformation. The fleeting transmetalation intermediate has been successfully synthesized through an alternative synthetic organometallic pathway at lower temperature, allowing for in situ NMR study of the C-N bond reductive elimination step. This study addresses key factors governing the mechanism of the nickel-catalyzed Buchwald-Hartwig amination process, thus improving the understanding of this important class of reactions.
- Bismuto, Alessandro,Delcaillau, Tristan,Müller, Patrick,Morandi, Bill
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p. 4630 - 4639
(2020/05/19)
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- Synthesis of unsymmetrically substituted triarylaminesviaacceptorless dehydrogenative aromatization using a Pd/C andp-toluenesulfonic acid hybrid relay catalyst
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An efficient and convenient procedure for synthesizing triarylamines based on a dehydrogenative aromatization strategy has been developed. A hybrid relay catalyst comprising carbon-supported Pd (Pd/C) andp-toluenesulfonic acid (TsOH) was found to be effective for synthesizing a variety of triarylamines bearing different aryl groups starting from arylamines (diarylamines or anilines), using cyclohexanones as the arylation sources under acceptorless conditions with the release of gaseous H2. The proposed reaction comprises the following relay steps: condensation of arylamines and cyclohexanones to produce imines or enamines, dehydrogenative aromatization of the imines or enamines over Pd nanoparticles (NPs), and elimination of H2from the Pd NPs. In this study, an interesting finding was obtained indicating that TsOH may promote the dehydrogenation.
- Jin, Xiongjie,Koizumi, Yu,Mizuno, Noritaka,Nozaki, Kyoko,Takayama, Satoshi,Yamaguchi, Kazuya,Yatabe, Takafumi
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p. 4074 - 4084
(2020/05/25)
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- A new copper complex on graphene oxide: A heterogeneous catalyst for N-arylation and C-H activation
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Graphene oxide supported Cu (II) ligand complex (GO?AP/L-Cu) has been synthesized and characterized by FT-IR, Raman, PXRD, UV–Visible, TGA, XPS, FESEM, TEM, EDAX, Elemental mapping, BET, CHNS and AAS analysis. The complex has been found to be efficient and reusable heterogeneous catalyst for the N-arylation and C-H activation reactions, both the catalytic reactions were found to be simple, cleaner and give high yields (~ 90%) of product. The catalyst can be easily filtered out from the reaction mixture and reused up to four times without significant loss of catalytic activity. The reported method is economical and novel in the sense that aqueous medium was used for both the reactions and for the stability of the catalyst. All isolated organic products were fully characterized on the basis of their physical and spectral data.
- Mittal, Ayushi,Kumari, Shweta,Parmanand,Yadav, Deepak,Sharma, Sunil K.
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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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- COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF
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The present invention relates to a device for emitting light. Provided are a novel mixture capable of improving stability and longevity, an organic electronic element using the same, and an electronic device thereof. (by machine translation)
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Paragraph 0335; 0437-0443
(2020/08/28)
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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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- 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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p. 15525 - 15538
(2019/10/19)
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- COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT COMPRISING THE SAME, AND ELECTRONIC DEVICE THEREOF
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Disclosed are an organic electroluminescent element comprising a compound represented by chemical formula 1 as a light emitting auxiliary layer material and an electronic device comprising the same. By comprising the compound represented by chemical formula 1 in a light emitting auxiliary layer, it is possible to lower a driving voltage, improve luminous efficiency, and expand lifespan of the organic electroluminescent element.COPYRIGHT KIPO 2019
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Paragraph 0111; 0116-0118; 0122; 0125; 0127; 0129
(2019/07/25)
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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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- Nano CoCuFe2O4-catalyzed coupling reaction of arylboronic acid with amines and thiols: An atom-economic and ligand-free route to access unsymmetrical amines and sulfides
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An efficient protocol was developed for the nano CoCuFe2O4-catalyzed C-N and C-S bond formation. By this catalytic system, both amine and sulfide-based structural motifs were formed efficiently in aryl halide-free route. The amination reaction of phenyl boronic acid with various types of amines was conducted under ligand-free conditions, in ethanol as a green solvent at 60°C. Unsymmetrical diaryl/aryl alkyl sulfide synthesis via the coupling reaction of arylboronic acids with thiols was also conducted. The nano cobalt-copper ferrite was used as a heterogenous efficient, inexpensive, magnetically separable and recyclable catalyst that can be used for several cycles.
- Moghaddam, Firouz Matloubi,Pourkaveh, Raheleh,Gholamtajari, Milad
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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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- Cu-doped CoFe2O4 nanoparticles as magnetically recoverable catalyst for C–N cross-coupling reaction
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A new hybrid catalyst has been developed by immobilizing copper acetate onto surface of cobalt ferrite magnetic nanoparticles bearing N–O chelating ligand. The magnetic core of the catalyst was synthesized via ultrasound assisted co-precipitation method and characterized by FT-IR, XRD, EDX, SEM, TEM, TGA and VSM analysis. The catalyst was found to be very active for C–N bond forming reaction. Coupling of amines and aryl boronic acid could be achieved in high yield in methanol in presence of triethylamine at room temperature. After completion of the reaction the catalyst could be recovered using an external magnet and reused for consecutive catalytic cycles without significant decrease in the catalytic activity.
- Dutta, Mintu Maan,Phukan, Prodeep
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- Cu(II) complex of phenylthiosemicarbazone: An in situ catalyst for formation of C-N bond between different N-based neucleophiles with arylboronic acids at room temperature
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We have reported here a new synthetic protocol for the formation of C-N bond catalyzed by a thiosemicarbazone complex of copper. This in situ complex has been found to be very effective for Chan-Lam C-N cross-coupling reaction of anilines and various imidazoles at room temperature. Pyrazole and 4-bromoindole were also activated for C-N bond formation by using this protocol at room temperature. This catalytic system gave good-to-excellent yield using a mixture of DMF and water as solvent in a 1:1 proportion.
- Gogoi, Nibedita,Borah, Geetika,Gogoi, Pradip K.
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- NIXANTPHOS: A highly active ligand for palladium catalyzed Buchwald-Hartwig amination of unactivated aryl chlorides
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Xantphos is one of the two most common ligands used in palladium catalyzed Buchwald-Hartwig amination reactions, because of its broad scope and high probability of success. It does not, however, work well with unactivated aryl chlorides. Herein NIXANTPHOS is compared to Xantphos and an array of mono- and bidentate phosphines. NIXANTPHOS outperforms Xantphos and all other bidentate ligands examined. Under the optimal reaction conditions, unactivated aryl chlorides afford the expected products in good to excellent yield with as low as 0.05 mol% (500 ppm) palladium loading.
- Mao, Jianyou,Zhang, Jiadi,Zhang, Shuguang,Walsh, Patrick J.
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supporting information
p. 8690 - 8696
(2018/07/13)
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- Method for preparing secondary aromatic amine or tertiary aromatic amine by conducting amination on aryl halide or alkyl halide
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The invention discloses a method for preparing secondary aromatic amine or tertiary aromatic amine by conducting amination on aryl halide or alkyl halide. That is to say, the alkyl halide or the arylhalide and organic amine are mixed according to a certain ratio, and under light irradiation, C-N coupling reaction is carried out, so that a corresponding target product is generated for preparing the secondary amine or the tertiary amine. Compared with existing synthesis technologies, the method has the advantages that the aryl halide or the alkyl halide which is cheap and easy to get is selected as a reaction substrate, the method has good universality for different organic amine separately, moreover, the product selectivity is high, and separation and purification are easy; moreover, the synthesis method does not need to be conducted under severe conditions of high temperature and the like, a green and sustainable light source is adopted as driving force, the atom economy is high, andthe method has wide application prospects.
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Paragraph 0029-0035; 0160; 0064; 0065; 0076; 0077; 0161
(2019/01/14)
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- Molecular Adsorbates Switch on Heterogeneous Catalysis: Induction of Reactivity by N-Heterocyclic Carbenes
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We report the N-heterocyclic carbene (NHC)-induced activation of an otherwise unreactive Pd/Al2O3 catalyst. Surface analysis techniques demonstrate the NHC being coordinated to the palladium particles and affecting their electronic properties. Ab initio calculations provide further insight into the electronic effect of the coordination with the NHC injecting electron density into the metal nanocluster thus lowering the barrier for bromobenzene activation. By this NHC modification, the catalyst could be successfully applied in the Buchwald-Hartwig amination of aryl chlorides, bromides, and iodides. Various heterogeneity tests could additionally show that the reaction proceeds via a heterogeneous active species.
- Ernst, Johannes B.,Schwermann, Christian,Yokota, Gen-Ichi,Tada, Mizuki,Muratsugu, Satoshi,Doltsinis, Nikos L.,Glorius, Frank
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supporting information
p. 9144 - 9147
(2017/07/22)
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- Synthesis of Triarylamines via Sequential C-N Bond Formation
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A one-pot domino N-arylation protocol is described using diaryliodonium reagents under copper catalysis. The reaction uses both aryl groups of the diaryliodonium reagent to generate triarylamines starting from simple anilines, representing an atom-economical preparation of an important class of organic material building blocks.
- Modha, Sachin G.,Popescu, Mihai V.,Greaney, Michael F.
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p. 11933 - 11938
(2017/11/24)
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- Versatile routes for synthesis of diarylamines through acceptorless dehydrogenative aromatization catalysis over supported gold-palladium bimetallic nanoparticles
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Diarylamines are an important class of widely utilized chemicals, and development of diverse procedures for their synthesis is of great importance. Herein, we have successfully developed novel versatile catalytic procedures for the synthesis of diarylamines through acceptorless dehydrogenative aromatization. In the presence of a gold-palladium alloy nanoparticle catalyst (Au-Pd/TiO2), various symmetrically substituted diarylamines could be synthesized starting from cyclohexylamines. The observed catalysis of Au-Pd/TiO2 was heterogeneous in nature and Au-Pd/TiO2 could be reused several times without severe loss of catalytic performance. This transformation needs no oxidants and generates molecular hydrogen (three equivalents with respect to cyclohexylamines) and ammonia as the side products. These features highlight the environmentally benign nature of the present transformation. Furthermore, in the presence of Au-Pd/TiO2, various kinds of structurally diverse unsymmetrically substituted diarylamines could successfully be synthesized starting from various combinations of substrates such as (i) anilines and cyclohexanones, (ii) cyclohexylamines and cyclohexanones, and (iii) nitrobenzenes and cyclohexanols. The role of the catalyst and the reaction pathways were investigated in detail for the transformation of cyclohexylamines. The catalytic performance was strongly influenced by the nature of the catalyst. In the presence of a supported gold nanoparticle catalyst (Au/TiO2), the desired diarylamines were hardly produced. Although a supported palladium nanoparticle catalyst (Pd/TiO2) gave the desired diarylamines, the catalytic activity was inferior to that of Au-Pd/TiO2. Moreover, the activity of Au-Pd/TiO2 was superior to that of a physical mixture of Au/TiO2 and Pd/TiO2. The present Au-Pd/TiO2-catalyzed transformation of cyclohexylamines proceeds through complex pathways comprising amine dehydrogenation, imine disproportionation, and condensation reactions. The amine dehydrogenation and imine disproportionation reactions are effectively promoted by palladium (not by gold), and the intrinsic catalytic performance of palladium is significantly improved by alloying with gold. One possible explanation of the alloying effect is the formation of electron-poor palladium species that can effectively promote the β-H elimination step in the rate-limiting amine dehydrogenation.
- Taniguchi, Kento,Jin, Xiongjie,Yamaguchi, Kazuya,Nozaki, Kyoko,Mizuno, Noritaka
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p. 2131 - 2142
(2017/03/09)
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- N/O-doped carbon as a "solid ligand" for nano-Pd catalyzed biphenyl- and triphenylamine syntheses
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A series of N/O-doped porous carbon supported nanopalladium catalysts have been successfully prepared, in which the N/O doped carbons were controllably produced via polypyrrole/furan synthesis followed by carbonization. These catalysts exhibit good performance in biphenylamine and triphenylamine syntheses with nitrobenzene and cyclohexanone as starting materials. Their catalytic activity can be tuned efficiently by the N/O functional groups on the carbon surface. TEM, XRD, XPS and laser Raman methods were applied to probe the structure of these catalysts. These results indicate that the Pd nanoparticles were supported on N/O-doped porous carbon via the "coordination" between Pd nanoparticles and N/O functional groups including O-CO, CN and tertiary nitrogen, and better catalytic performance was obtained if carbon with the highest N-species loading was used as the support. In addition, a mechanistic study proved that the reaction starts with the catalytic reduction of nitrobenzene with cyclohexanone as the hydrogen source. During this reaction, aniline was formed and the cyclohexanone was transformed into phenol. Then biphenylamine and triphenylamine were generated through the reaction of aniline and cyclohexanone. This work should facilitate the controllable preparation of carbon supported nanocatalysts with specific activity, and open up a promising pathway for the development of new methodologies for N-containing fine chemical synthesis.
- Pang, Shaofeng,Zhang, Yujing,Huang, Yongji,Yuan, Hangkong,Shi, Feng
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p. 2170 - 2182
(2017/07/24)
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- Organonickel complexes encumbering bis-imidazolylidene carbene ligands: Synthesis, X-ray structure and catalytic insights on Buchwald-Hartwig amination reactions
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New four coordinated homoleptic bis(diimidazolylidene)nickel(II) complexes (C1 & C2) were synthesized and characterized by elemental analysis, NMR (1H and13C) as well as ESI-Mass spectrometry. The molecular structure of the complex C1 was identified by means of single-crystal X-ray diffraction analysis, which revealed that the complexes possess a distorted square planar geometry with chelating bis(diimidazolylidene) NHC ligands and two non coordinating bromide counter ions in tetradentate C4fashion. A survey of their catalytic activity in Buchwald?Hartwig amination has been performed. The newly synthesized complexes also catalyzed the amination of aryl chlorides in the presence of KOtBu. Various aryl chlorides and amines can react smoothly to give the corresponding aminated products in moderate to high yields. The scope of the reaction encompasses electronically varied aryl chlorides and nitrogen-containing heteroaryl chlorides, including pyridine and quinoline derivatives. Both secondary and primary amines are well tolerated under the optimal reaction conditions.
- Nirmala, Muthukumaran,Saranya, Gandhi,Viswanathamurthi, Periasamy,Bertani, Roberta,Sgarbossa, Paolo,Malecki, Jan Grzegorz
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supporting information
p. 1 - 10
(2017/01/09)
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- Application of a 2-aryl indenylphosphine ligand in the Buchwald-Hartwig cross-coupling reactions of aryl and heteroaryl chlorides under the solvent-free and aqueous conditions
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An efficient solvent-free protocol for the Buchwald-Hartwig cross-coupling reaction of aryl and heteroaryl chlorides with primary and secondary amines using the Pd(dba)2/ligand 1 catalytic system has been developed. Notably, the catalytic system also efficiently catalyzed the reaction under aqueous conditions.
- Liu, Yan,Yuan, Jia,Wang, Zi-Fei,Zeng, Si-Hao,Gao, Meng-Yue,Ruan, Mei-Lin,Chen, Jian,Yu, Guang-Ao
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supporting information
p. 5805 - 5810
(2017/07/22)
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- Method of manufacturing hydroxytriarylamine compd.
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PROBLEM TO BE SOLVED: To provide a method for producing an arylamine compound, capable of avoiding bumping during reaction even with a reduced amount of reaction solvent, increasing an amount obtained per one batch, achieving excellent productivity, and producing an arylamine compound of high quality at a low cost.SOLUTION: In a method for producing an arylamine compound, an aryl halide compound and an amine compound are reacted in presence of a palladium catalyst and at least one base selected from alkali metal hydroxide and alkaline earth metal hydroxide, while distilling off by-produced water.
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Paragraph 0052-0055; 0066
(2018/03/13)
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- Palladium-Catalyzed N-Arylation of Amines and Amides with Aryltrimethylgermanes
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Described herein is a novel palladium-catalyzed C-N bond-formation reaction employing aryltrimethylgermanes as the new arylating reagents. Primary/secondary amines or even amides could be smoothly arylated to provide the corresponding N-arylation products in moderate to excellent yields.
- Zhang, Qiang,Liu, Cunfang,Shi, Juan,Xu, Qiong,Jin, Lingxia,Zhao, Chaibin,Zhang, Tianlei
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supporting information
p. 1945 - 1948
(2016/08/09)
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- A method for preparing aromatic amine derivative
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The invention discloses a preparation method of a diarylamine ramification. The preparation method comprises the following steps: dissolving a phenylamine ramification, a phenylhydrazine ramification, a metal phthalocyanine ramification and a copper salt into a solvent, and reacting at -10 to 40 DEG C to obtain the diarylamine ramification. According to the preparation method, the phenylamine ramification and the phenylhydrazine ramification are taken as starting materials, so that raw materials are easy to obtain and plenty in variety; a product obtained by utilizing the method is plenty in type, can not only be directly used, but also be used for other further reactions; and no additive is required to be added. The preparation method disclosed by the invention has the advantages of short synthetic route, moderation in reaction condition, simple reaction operation and post-processing process, high yield and suitability for large-scale production.
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Paragraph 0151-0154
(2016/10/08)
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- CoPc/Cu(OAc)2-catalyzed N-arylation of amines with arylhydrazines leading to N-aryl amines
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The N-arylation of amines with arylhydrazines has been developed, achieving the selective cross-coupling of aryl radicals with amines to form N-aryl amines. The reaction uses air as an oxidant, CoPc and Cu(OAc)2as catalysts. The reaction proceeds under mild conditions in air through a relay process, arylhydrazines are oxidized to aryldiazenes by CoPc, further oxidized to aryl radicals by air (O2), which are trapped by Cu(OAc)2–amine complex, followed by reduction–elimination reaction to form N-aryl amines. Arylamines and arylhydrazines give the highest yields, but N-aryl-N-alkylamines and N-alkylamines can be used as well.
- Sun, Wang-Bin,Zhang, Pei-Zhi,Jiang, Tao,Li, Cheng-Kun,An, Li-Tao,Shoberu, Adedamola,Zou, Jian-Ping
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p. 6477 - 6483
(2016/09/23)
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- Facile access to: N -substituted anilines via dehydrogenative aromatization catalysis over supported gold-palladium bimetallic nanoparticles
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N-Substituted anilines are widely utilized important compounds, and the development of their diverse synthetic procedures is of great significance. Herein, we have successfully developed a widely applicable powerful catalytic route to N-substituted anilines. In the presence of a gold-palladium alloy nanoparticle catalyst (Au-Pd/Al2O3) and styrene, various kinds of structurally diverse N-substituted anilines (twenty three examples) could be synthesized starting from cyclohexanones and amines (including aliphatic primary and secondary amines and anilines). The catalytic performance was strongly influenced by the nature of the catalyst. A supported gold catalyst (Au/Al2O3) was completely inactive for the present transformation. Although a supported palladium catalyst (Pd/Al2O3) gave the desired N-substituted anilines to some extent, the performance was inferior to that of Au-Pd/Al2O3. The catalytic activity of the palladium species in Au-Pd/Al2O3 was at least ca. three times higher than that in Pd/Al2O3. Moreover, the performance of Au-Pd/Al2O3 was superior to that of a physical mixture of Au/Al2O3 and Pd/Al2O3. Thus, palladium was intrinsically effective for the present transformation (dehydrogenative aromatization) and its performance was improved by alloying with gold. The present transformation proceeds through a sequence of the dehydrative condensation of cyclohexanones and amines to produce enamines (or ketimines), followed by the dehydrogenative aromatization to produce the corresponding N-substituted anilines. In the aromatization step, styrene could act as an effective hydrogen acceptor to selectively produce the desired N-substituted anilines without catalyzing the disproportionation of the enamine intermediates. The observed catalysis using Au-Pd/Al2O3 was truly heterogeneous in nature, and Au-Pd/Al2O3 could be reused.
- Taniguchi, Kento,Jin, Xiongjie,Yamaguchi, Kazuya,Mizuno, Noritaka
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p. 3929 - 3937
(2016/06/14)
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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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- An easily available N-heterocyclic carbene–palladium(II) catalyst for Buchwald–Hartwig amination of aryl chlorides
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Abstract: An easily available N-heterocyclic carbene–palladium(II) complex was found to be an efficient catalyst for the Buchwald–Hartwig amination of aryl chlorides. Both secondary and primary amines were tolerated under the same reaction conditions. Under the optimal conditions, all reactions proceeded successfully to give the desired products in good to high yields within hours. Graphical Abstract: [Figure not available: see fulltext.]
- Wang, Tao,Xu, Kai,Liu, Lantao,Xie, Huanping,Li, Ying,Zhao, Wen-Xian
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p. 525 - 529
(2016/07/20)
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- N-(Pyridin-2-yl)benzamide: Efficient ligand for the nickel catalyzed Chan-Lam cross-coupling reaction
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An efficient protocol for the Chan-Lam cross-coupling reactions of arylboronic acids with aryl or alkyl amines has been developed by employing simple N-(pyridin-2-yl)benzamide ligand with Ni(OAc)2·4H2O in the presence of TMG base. The reaction proceeded well with high yields by employing various N-nucleophiles at low catalytic loadings.
- Keesara, Srinivas
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p. 6685 - 6688
(2016/01/28)
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- Synthesis and development of Chitosan anchored copper(II) Schiff base complexes as heterogeneous catalysts for N-arylation of amines
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Abstract The Chitosan anchored Cu(II) Schiff base complexes (C1-C3) have been synthesized and characterized by FTIR, UV, FE-SEM, EDAX, TGA, AAS and elemental analysis. These complexes have been found to be efficient and recyclable heterogeneous catalysts for the Chan-Lam C-N coupling reaction of various aromatic/aliphatic amines with arylboronic acid under mild reaction conditions. These complexes can be easily filtered out from the reaction medium and reused up to five times without significant loss of catalytic activity.
- Anuradha,Kumari, Shweta,Pathak, Devendra D.
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supporting information
p. 4135 - 4142
(2015/08/03)
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- Nickel(II) complex incorporating methylene bridged tetradentate dicarbene ligand as an efficient catalyst toward CC and CN bond formation reactions
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For the evaluation of binding and catalytic nature of N-heterocyclic carbenes (NHCs) and their complexes, a new methylene bridged bis(aryloxy-NHC) ligand has been prepared. A novel air-stable Ni(II) complex bearing the new NHC ligand has been synthesized and characterized by elemental analysis, NMR (1H and 13C) as well as ESI-mass spectrometry. The molecular structure of the complex was identified by means of single crystal X-ray diffraction analysis which revealed that the Ni(II) complex possesses a square planar geometry with the ligand coordinating with bi-negative tetradentate C2O2 fashion and the complex showed efficient catalytic activity toward the Suzuki-Miyaura cross-coupling reaction between aryl halides and arylboronic acids under phosphine free conditions. The new complex also catalyzed the amination of aryl chlorides in the presence of KOtBu. Various aryl chlorides and amines can react smoothly to give the corresponding aminated products in moderate to high yields. Both secondary and primary amines are well tolerated under the optimal reaction conditions.
- Nirmala, Muthukumaran,Prakash, Govindan,Ramachandran, Rangasamy,Viswanathamurthi, Periasamy,Malecki, Jan Grzegorz,Linert, Wolfgang
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- 2,6-Bis(diphenylphosphino)pyridine: A simple ligand showing high performance in palladium-catalyzed CN coupling reactions
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The use of commercially available 2,6-bis(diphenylphosphino)pyridine as a ligand in conjunction with K2CO3, DMAc and TBAB is an effective method for the palladium-catalyzed CN coupling of a variety of aryl halides with anilines, N-heterocyclic aromatic amines, and a cyclic secondary amine. The reactions proceed in good to excellent yield (up to 98%) while the loading of Pd(OAc)2 was as low as 0.025 mol %.
- Nadri, Shirin,Rafiee, Ezzat,Jamali, Sirous,Joshaghani, Mohammad
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p. 4098 - 4101
(2014/07/22)
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- Palladium-catalyzed amination of aryl sulfides with anilines
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A combination of a palladium-NHC catalyst and potassium hexamethyldisilazide enables the amination of aryl sulfides with anilines to afford a wide variety of diarylamines. The reaction conditions are versatile enough for the reaction of even bulky ortho-substituted aryl sulfides. This amination can be applied to the modular synthesis of N-aryl carbazoles from the corresponding ortho-bromothioanisoles. As aryl sulfoxides undergo extended Pummerer reactions to afford ortho-substituted aryl sulfides, the Pummerer products are thus useful substrates for the amination to culminate in efficient syntheses of a 2-anilinobenzothiophene and an indole as proof-of-principle of the utility of the extended Pummerer reaction/amination cascade. Switching S to N: Transformation of inert C-S bonds of aryl sulfides into C-N bonds is achieved using a palladium complex with an N-heterocyclic carbene ligand. Thanks to the efficient conditions for amination of bulky sulfides, the synthesis of carbazole products from 2-biphenylylamine is achieved through oxidative C-N bond formation. When combined with extended Pummerer reactions, intriguing nitrogen-containing molecules are prepared.
- Sugahara, Tomohiro,Murakami, Kei,Yorimitsu, Hideki,Osuka, Atsuhiro
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supporting information
p. 9329 - 9333,5
(2014/11/07)
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- Visible light-driven cross-coupling reactions at lower temperatures using a photocatalyst of palladium and gold alloy nanoparticles
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Palladium (Pd)-catalyzed cross-coupling reactions are among the most important methods in organic synthesis. We report the discovery of highly efficient and green photocatalytic processes by which cross-coupling reactions, including Sonogashira, Stille, Hiyama, Ullmann, and Buchwald-Hartwig reactions, can be driven with visible light at temperatures slightly above room temperature using alloy nanoparticles of gold and Pd on zirconium oxide, thus achieving high yields. The alloy nanoparticles absorb visible light, and their conduction electrons gain energy, which is available at the surface Pd sites. Results of the density functional theory calculations indicate that transfer of the light excited electrons from the nanoparticle surface to the reactant molecules adsorbed on the nanoparticle surface activates the reactants. When the light intensity was increased, a higher reaction rate was observed, because of the increased population of photoexcited electrons. The irradiation wavelength also has an important impact on the reaction rates. Ultraviolet irradiation can drive some reactions with the chlorobenzene substrate, while visible light irradiation failed to, and substantially improve the yields of the reactions with the bromobenzene substrate. The discovery reveals the possibility of using low-energy and -density sources such as sunlight to drive chemical transformations.
- Xiao, Qi,Sarina, Sarina,Bo, Arixin,Jia, Jianfeng,Liu, Hongwei,Arnold, Dennis P.,Huang, Yiming,Wu, Haishun,Zhu, Huaiyong
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p. 1725 - 1734
(2014/06/24)
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- Ligand-free CuTC-catalyzed N-arylation of amides, anilines and 4-aminoantipyrine: Synthesis of N-arylacrylamides, 4-amido-N-phenylbenzamides and 4-amino(N-phenyl)antipyrenes
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N-Arylation of amides and anilines with aryl iodides was efficiently catalyzed by copper thiophenecarboxylate under ligand-free conditions with good to excellent yields. A variety of substituted aryl iodides, amides, anilines and 4-aminoantipyrine were found to be applicable to the simple catalytic system. Furthermore, some practical, unique secondary amides, such as N-arylacrylamides and 4-amido-N-phenylbenzamides, and 4-amino(N-phenyl)antipyrenes, which are difficult to obtain by the classical methods, were prepared.
- Quan, Zheng-Jun,Xia, Hai-Dong,Zhang, Zhang,Da, Yu-Xia,Wang, Xi-Cun
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- Unique copper-salen complex: An efficient catalyst for N-arylations of anilines and imidazoles at room temperature
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We have reported here the catalytic activity of a unique Cu-salen type complex in N-arylation of anilines with arylboronic acids in water. The protocol is found to be applicable for a wide range of electronically diversified arylboronic acids and anilines with excellent yields of the isolated product. Further the scope of this protocol has been extended to the synthesis of various N-aryl imidazoles in iso-propanol.
- Gogoi, Ankur,Sarmah, Gayatri,Dewan, Anindita,Bora, Utpal
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- N-heterocyclic carbene-palladium(II)-4,5-dihydrooxazole complexes: Synthesis and catalytic activity toward amination of aryl chlorides
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A series of novel N-heterocyclic carbene-palladium(II)-4,5-dihydrooxazole (NHC-PdII-Ox) complexes 3 were successfully synthesized from commercially available imidazolium salts 1, PdCl2, and 4,5-dihydrooxazoles 2 in a one-step process, and these complexes showed efficient catalytic activity toward the amination of aryl chlorides. Both secondary and primary amines were tolerated under the same reaction conditions. Under the optimal reaction conditions, the expected coupling products were obtained in moderate to high yields.
- Huang, Pei,Wang, Yi-Xiang,Yu, Hong-Fei,Lu, Jian-Mei
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supporting information
p. 1587 - 1593
(2014/05/06)
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- A mild and catalyst-free aromatization using dihydroxylcyclohexanone derivatives as phenyl sources: A new approach to anilines
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A new and efficient protocol for the preparation of N-substituted anilines via an aromatization reaction was developed. 3,5-Dihydroxylcyclohexanone derivatives were used as the sources of the phenyl group and reacted smoothly with primary or secondary amines under mild conditions in the absence of metal catalyst and strong base. A variety of N-substituted anilines were prepared by this method with excellent yields up to 99%. The results indicate that this reaction begins with a nucleophilic addition.
- Luo, Jun,Ji, Enwei,Ye, Jingyuan,Wu, Runze,Qiu, Lei
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p. 4505 - 4508
(2013/08/23)
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- N-arylation of amines with o-silylaryl triflate
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An efficient, transition-metal-free procedure for the N-arylation of amines 1 has been achieved by allowing those substrates to react with o-silylaryl triflate 2 in the presence of CsF. Good to excellent yields of arylated products 3 are obtained under very mild reaction conditions. This chemistry readily tolerates a variety of functional groups.
- Lee,Jung,Hahn
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p. 6690 - 6692
(2013/07/26)
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- Pd-catalyzed synthesis of aryl amines via oxidative aromatization of cyclic ketones and amines with molecular oxygen
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Pd-catalyzed intermolecular aerobic dehydrogenative aromatizations have been developed for the arylation of amines with nonaromatic ketones. Under optimized reaction conditions, primary and secondary amines are selectively arylated in good yields with cyclohexanones and 2-cyclohexen-1-ones in the presence of a Pd-catalyst under an atmosphere of molecular oxygen.
- Girard, Simon A.,Knauber, Thomas,Zhou, Feng,Simon, Marc-Olivier,Li, Chao-Jun,Hu, Xiong,Deng, Guo-Jun
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supporting information
p. 5606 - 5609,4
(2012/12/12)
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- Nickel-mediated N-arylation with arylboronic acids: An avenue to Chan-Lam coupling
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An efficient use of NiCl2·6H2O, for the cross-coupling of arylboronic acids with various N-nucleophiles, has been demonstrated. The method is practical and offers an alternative to the corresponding Cu-mediated Chan-Lam process for the construction of the C-N bond.
- Raghuvanshi, Dushyant Singh,Gupta, Amit Kumar,Singh, Krishna Nand
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supporting information
p. 4326 - 4329
(2012/10/29)
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- Palladium-catalyzed one-pot diarylamine formation from nitroarenes and cyclohexanones
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The first palladium-catalyzed diarylamine formation from nitroarenes and cyclohexanone derivatives using borrowed hydrogen is described. Various diarylamines were selectively obtained in good to excellent yields. The reaction tolerated a wide range of functionalities. The nitro reduction, cyclohexanone dehydrogenation, and imine formation and reduction were realized in a cascade without an external reducing reagent and oxidant.
- Xie, Yanjun,Liu, Saiwen,Liu, Yong,Wen, Yuqing,Deng, Guo-Jun
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supporting information; experimental part
p. 1692 - 1695
(2012/06/18)
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- Well-defined NHC-Pd(II)-Im (NHC=N-heterocyclic carbene; Im=1-methylimidazole) complex catalyzed C-N coupling of primary amines with aryl chlorides
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We report herein a well-defined NHC-Pd(II)-Im (NHC=N-heterocyclic carbene; Im=1-methylimidazole) complex catalyzed C-N coupling of primary amines with aryl chlorides. Under the optimal reaction conditions, a variety of primary amines can be coupled with aryl chlorides to give the amination products in good to high yields within 4 h. It is worthy of noting here that the NHC-Pd(II)-Im complex showed especially high catalytic activity toward challenging sterically hindered substrates including both of aryl amines and aryl chlorides. In addition, alkyl amines were also proved to be suitable reaction partners to give the corresponding amination products in good to high yields.
- Zhu, Lei,Ye, Yue-Mei,Shao, Li-Xiong
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experimental part
p. 2414 - 2420
(2012/04/10)
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- Triphenylphosphine as a ligand for the Pd-catalyzed amination of unactivated aryl chlorides with anilines promoted by salicylaldimine
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An efficient and selective amination of unactivated aryl chlorides with anilines catalyzed by mixed ligand Pd catalytic system of Ph3P- salicylaldimine has been developed for the preparation of diarylamines. The benzyne mechanism was ruled out based on experimental results. Georg Thieme Verlag Stuttgart · New York.
- Liu, Tao-Ping,Cheng, Qiang,Song, Wen-Jing,Cai, Liang-Zhen,Tao, Xiao-Chun
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supporting information
p. 2333 - 2336
(2013/07/19)
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- NOVEL CATALYSTS
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The present invention provides novel compounds and ligands that are useful in transition metal catalyzed cross-coupling reactions. For example, the compounds and ligands of the present invention are useful in palladium or gold catalyzed cross-coupling reactions.
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Page/Page column 66
(2012/06/01)
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