- 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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- Synthesis and characterization of new square planar heteroleptic cationic complexes [Ni(ii) β-oxodithioester-dppe]+; Their use as a catalyst for Chan-Lam coupling
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Novel heteroleptic [Ni(ii) β-oxodithioester-dppe]+PF6- complexes (β-oxodithioester = methyl-3-hydroxy-3-benzyl-2-propenedithioate L1 1, methyl-3-hydroxy-3-(p-methoxyphenyl)-2-propenedithioate L2 2, methyl-3-hydroxy-3-(naphthyl)-2-propenedithioate L3 3, methyl-3-hydroxy-3-(p-chlorophenyl)-2-propenedithioate L4 4, methyl-3-hydroxy-3-(p-bromophenyl)-2-propenedithioate L5 5 and methyl-3-hydroxy-3-(p-cyanophenyl)-2-propenedithioate L6 6) have been synthesized and characterized by elemental (C, H, N) analysis, ESI-MS, IR, UV-visible, 1H, 13C{1H}, 31P{1H} and 19F{1H} NMR spectroscopy. The distorted square planar structures of the isomorphous cationic complexes 2, 3, 4 and 5 have been determined by X-ray crystallography. The catalytic activities of 1-6 were investigated for the Chan-Lam coupling reaction involving arylboronic acids and amines to afford N-arylated products in good to excellent yields under mild conditions with 1 mol% catalyst loading. This catalytic protocol offers significant functional group tolerance, and is endowed with a broad substrate scope. This journal is
- Kumari, Kavita,Kumar, Saurabh,Singh, Krishna Nand,Drew, Michael G. B.,Singh, Nanhai
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p. 12143 - 12153
(2020/07/30)
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- Well-Designed N-Heterocyclic Carbene Ligands for Palladium-Catalyzed Denitrative C-N Coupling of Nitroarenes with Amines
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The C-N bond formation is one of the fundamental reactions in organic chemistry, because of the widespread presence of amine moieties in pharmaceuticals and biologically active compounds. Palladium-catalyzed C-N coupling of haloarenes represents one of the most efficient approaches to aromatic amines. Nitroarenes are ideal alternative electrophilic coupling partners, since they are inexpensive and readily available. The denitration and cross-coupling using nitroarenes as the electrophilic partners is challenging, because of the low reactivity of the Ar-NO2 bond toward oxidative addition. We report here the C-N coupling of nitroarenes and amines using palladium/5-(2,4,6-triisopropylphenyl)imidazolylidene[1,5-a]pyridines as the catalyst. The ligands are readily available from commercial chemicals. The reaction shows broad substrate scope and functional group tolerance. The method is applicable to both aromatic and aliphatic amines, and many secondary and tertiary aromatic amines bearing various functional groups were obtained in high yields.
- Chen, Kai,Chen, Wanzhi,Chen, Wei,Liu, Miaochang,Wu, Huayue
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p. 8110 - 8115
(2019/08/26)
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- Palladium-catalyzed c(sp2)-n bond cross-coupling with triaryl phosphates
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The first general palladium-catalyzed amination of aryl phosphates is described. The combination of MorDalPhos with [Pd(-cinnamyl)Cl]2 enables the amination of electron-rich, electron-neutral, and electron-poor aryl phosphates with a board range of aromatic, aliphatic, and heterocyclic amines. Common functional groups such as ether, keto, ester, and nitrile show an excellent compatibility in this reaction condition. The solvent-free amination reactions are also successful in both solid coupling partners. The gram-scale cross-coupling is achieved by this catalytic system.
- Chen, Zicong,Chen, Xiangmeng,So, Chau Ming
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- Palladium-Catalyzed C(sp2)-N Bond Cross-Coupling with Triaryl Phosphates
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The first general palladium-catalyzed amination of aryl phosphates is described. The combination of MorDalPhos with [Pd(?-cinnamyl)Cl]2 enables the amination of electron-rich, electron-neutral, and electron-poor aryl phosphates with a board range of aromatic, aliphatic, and heterocyclic amines. Common functional groups such as ether, keto, ester, and nitrile show an excellent compatibility in this reaction condition. The solvent-free amination reactions are also successful in both solid coupling partners. The gram-scale cross-coupling is achieved by this catalytic system.
- Chen, Zicong,Chen, Xiangmeng,So, Chau Ming
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p. 6366 - 6376
(2019/05/24)
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- Insights on bimetallic micellar nanocatalysis for buchwald-hartwig aminations
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A nanocatalyst for micellar Buchwald-Hartwig aminations is developed, thoroughly characterized, and applied on a variety of substrates. The catalyst is stable under ambient conditions for at least six months. The catalyst retained its activity after several cycles, and its structure remained intact as confirmed by NMR spectroscopy. Association of Pd nanoparticles with Cu by a phosphine ligand is revealed by 31P NMR spectroscopy, and their linkage with the activated carbon surface is revealed by XAS analysis. Control NMR experiments revealed the binding of the ligand with both Cu and Pd, and all phosphine molecules are under the same environment. In addition to NMR and XAS analysis, the catalyst is characterized by SEM, HRTEM, XPS, and TGA. Reactions are highly reproducible at variable scales. Environmentally benign, proline-based amphiphile PS-750-M is critical for catalytic activity, which is achieved under mild conditions in water as the reaction medium. The inherent sustainability of these conditions coupled with a low E factor achievable through robust recycling of catalyst and reaction medium demonstrates the significant utility of this technology.
- Ansari, Tharique N.,Taussat, Armand,Clark, Adam H.,Nachtegaal, Maarten,Plummer, Scott,Gallou, Fabrice,Handa, Sachin
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p. 10389 - 10397
(2019/10/14)
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- Method for synthesizing diarylamine by optical/nickel concerted catalysis
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The invention discloses a method for synthesizing diarylamine by optical/nickel concerted catalysis. According to the method, a ligand does not need to be added, and simple and cheap nickel salt is directly used as a metal catalyst to cooperate with a photosensitizer to catalyze arylamine and aryl bromide to generate cross-coupling. The method has the following advantages: (1) the use amount of BODIPY type organic photocatalyst is low, and the BODIPY type organic photocatalyst has a better catalysis effect in comparison with metal iridium and ruthenium photocatalysts reported in the literature; (2) the BODIPY type organic photocatalyst is easy for synthesis; (3) the use amount of nickel salt is few, and the ligand does not need to be added; and (4) the reaction conditions are mild, and theyield of most coupling products is higher than 90%. According to the method disclosed by the invention, high temperature and high pressure equipment is not needed, temperature change scope is small,experimental procedure is simple and easy to operate, and the method has a relatively high application value and industrial popularization potential.
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Paragraph 0046; 0047; 0048; 0049; 0108; 0109; 0110; 0111
(2018/09/08)
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- COMPOUND FOR ORGANIC ELECTROLUMINESCENT DEVICE AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
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The present invention refers to and preparation of that for organic electroluminescent device including under public affairs which number organic electroluminescence device, the fluorescent of light-emitting material purity and and light emitting efficien
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Paragraph 0379-0381
(2016/10/10)
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- COMPOUND FOR ORGANIC ELECTROLUMINESCENT DEVICE AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
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Provided in the present invention are a compound for an organic electroluminescent device and an organic electroluminescent device comprising the same. Accordingly, provided are the organic electroluminescent device used as a dopant of a light emitting la
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Paragraph 0179-0181
(2016/10/27)
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- COMPOUND FOR ORGANIC ELECTROLUMINESCENT DEVICE AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
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Provided are a compound for an organic electroluminescent device, and an organic electroluminescent device comprising the same. The compound for an organic electroluminescent device can be used as a dopant of a luminous layer, which can enhance color puri
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Paragraph 0187-0189
(2017/01/09)
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- Aromatic amine-Tercyclohexane phenylpropionic compd. and use thereof in the organic semiconductor component
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The present invention relates to aromatic amine-terphenyl compounds and use thereof in organic semiconducting components. The organic semiconducting components may contain at least one layer that includes one or more of the aromatic amine-terphenyl compou
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Paragraph 0079
(2016/11/21)
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- B(C6F5)3-catalyzed metal-free hydrogenation of naphthylamines
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A catalytic metal-free hydrogenation of naphthylamines using B(C6F5)3 as a catalyst was successfully achieved under mild conditions for the first time to furnish a variety of tetrahydronaphthylamines in 88-99% yields.
- Li, Gen,Liu, Yongbing,Du, Haifeng
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supporting information
p. 2875 - 2878
(2015/04/27)
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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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- Facile synthesis of Fe@Pd nanowires and their catalytic activity in ligand-free CN bond formation in water
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This work reports a facile synthesis of Fe@Pd nanowires. Ligand-free cross coupling reactions of arylboronic acids with various amines in aqueous medium proceed in very good to excellent yield with the use of Fe@Pd nanowires. Furthermore, the catalyst could be easily separated from the reaction mixture using a magnet and could be recycled several times without loss of catalytic activity.
- Nasrollahzadeh, Mahmoud,Azarian, Abbas,Ehsani, Ali,Zahraei, Ali
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p. 2813 - 2817
(2014/05/06)
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- Stable nickel(0) phosphites as catalysts for C-N cross-coupling reactions
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Herein we describe the design and preparation of inexpensive, air-stable nickel phosphite-based catalysts for use in the C-N cross-coupling reaction. The combination of nickel tetrakis(triphenyl phosphite) {Ni[P(OPh) 3]4} and 1,1'-bis(diphenylphosphino)ferrocene (dppf), and in particular a newly developed catalyst (dppf)Ni[P(OPh)3] 2, were found to be extremely effective in catalyzing a range of amination reactions of anilines and amines with aryl chlorides. This new catalyst system offers an alternative to the bis(cyclooctadienyl)nickel [Ni(COD)2] and palladium(0) catalysts commonly used for C-N bond formation.
- Kampmann, Sven S.,Sobolev, Alexandre N.,Koutsantonis, George A.,Stewart, Scott G.
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supporting information
p. 1967 - 1973
(2014/07/07)
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- One-pot synthesis of diarylamines from two aromatic amines via oxidative dearomatization-imino exchange-reductive aromatization
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A one-pot synthetic strategy for diarylamines using only aromatic amines as starting materials has been developed. This method involved a PhI(OAc) 2-induced oxidative dearomatization of N-sulfonyl protected para-substituted anilines, a Bi(OTf)3-catalyzed imino exchange reaction between N-sulfonyl cyclohexadienimines and aromatic amines, and a CF3COOH/Zn mediated reductive aromatization of the resulting N-aryl cyclohexadienimines.
- Zhang, Li,Wang, Weibin,Fan, Renhua
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supporting information
p. 2018 - 2021
(2013/05/23)
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- Recyclable catalysts for palladium-catalyzed aminations of aryl halides
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Aminated and recycled: Palladium/imidazolium phosphane catalysts enable efficient and general aminations of aryl halides, including direct amination with ammonia. Subsequent recycling is possible without any additional heterogenization (see scheme).
- Dumrath, Andreas,Luebbe, Christa,Neumann, Helfried,Jackstell, Ralf,Beller, Matthias
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experimental part
p. 9599 - 9604
(2011/10/04)
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- Palladium-catalyzed amination of aryl and heteroaryl tosylates at room temperature
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Mild palladium-catalyzed aminations of aryl tosylates and the first aminations of heteroaryl tosylates are described. In the presence of the combination of L2Pd(0) (L = P(o-tol)3) and the hindered Josiphos ligand CyPF-t-Bu, a variety of primary alkylamines and arylamines react with both aryl and heteroaryl tosylates at room temperature to form the corresponding secondary arylamines in high yields with complete selectivity for the monoarylamine. These reactions at room temperature occur in many cases with catalyst loadings of 0.1 mol % and 0.01 mol % in one case, constituting the most efficient aminations of aryl tosylates by nearly 2 orders of magnitude. This catalyst is made practical by the development of a convenient method to synthesize the L2Pd(0) precursor. This complex is stable to air as a solid. In contrast to conventional relative rates for reactions of aryl sulfonates, the reactions of aryl tosylates are faster than parallel reactions of aryl triflates, and the reactions of aryl tosylates are faster than parallel or competitive reactions of aryl chlorides. Copyright
- Ogata, Tokutaro,Hartwig, John F.
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supporting information; experimental part
p. 13848 - 13849
(2009/02/07)
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- Nickel-catalyzed amination of aryl tosylates
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(Chemical Equation Presented) The cross-coupling of aryl tosylates with amines and anilines was accomplished by using a Ni-based catalyst system from the combination of Ni(II)-(σ-aryl) complexes/N-heterocyclic carbenes (NHCs). The feature, scope, and limitation of this reaction are disclosed.
- Gao, Cai-Yan,Yang, Lian-Ming
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p. 1624 - 1627
(2008/09/17)
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- Amination of aryl chlorides in water catalyzed by cyclopalladated ferrocenylimine complexes with commercially available monophosphinobiaryl ligands
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The easily accessible, air- and moisture-stable cyclopalladated ferrocenylimine complex 3 was found to be a highly active one-component precatalyst for the amination of aryl chlorides in water in the presence of inexpensive KOH and t-BuOH as a base and an additive, respectively.
- Xu, Chen,Gong, Jun-Fang,Wu, Yang-Jie
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p. 1619 - 1623
(2008/01/27)
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