- Benzyloxycalix[8]arene supported Pd-NHC cinnamyl complexes for Buchwald-Hartwig C-N cross-couplings
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The scalable synthesis of Pd-NHC cinnamyl complexes supported on benzyloxycalix[8]arene is reported. These catalysts are very active for Buchwald-Hartwig cross-coupling reactions, allowing the coupling of aryl chlorides and bromides with a wide variety of alkyl and aryl amines using low catalytic loadings. The supported complexes also successfully afforded attractive unsymmetrical triarylamines, and in one case, promoted the synthesis of an unprecedented Pd-catalyzed C-H activation product. Thanks to the calixarenic support, the target products could be isolated with low levels of residual palladium, and in some cases, even below the restrictive toxic metal standards applied by the pharmaceutical industry. Through an easy to implement procedure, these perfectly characterised catalysts thus combine the best of homogeneous and heterogeneous catalysis: high efficiency (similar to or even better than the corresponding homogeneous complexes) and low Pd leaching levels expected from heterogeneous catalysts.
- Abi Fayssal, Sandra,Buendia, Julien,Huc, Vincent,Martini, Cyril,Naret, Timothée,Schulz, Emmanuelle
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p. 5223 - 5231
(2021/08/16)
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- Transition-Metal-Free Diarylation of Isocyanates with Arynes
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A facile method for the transition-metal-free diarylation of isocyanates with arynes in the presence of cesium fluoride has been developed, which affords functionalized diaryl amines in moderate to excellent yields. This reaction has good functional group tolerance and provides excellent regioselectivity by utilizing a methoxy-substituted aryne precursor.
- Jang, Woo Cheol,Hwang, Dong Wook,Seo, Jeong Hoon,Ko, Haye Min
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supporting information
(2019/08/30)
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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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- Buchwald–Hartwig Amination of Nitroarenes
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The Buchwald–Hartwig amination of nitroarenes was achieved for the first time by using palladium catalysts bearing dialkyl(biaryl)phosphine ligands. These cross-coupling reactions of nitroarenes with diarylamines, arylamines, and alkylamines afforded the corresponding substituted arylamines. A catalytic cycle involving the oxidative addition of the Ar?NO2 bond to palladium(0) followed by nitrite/amine exchange is proposed based on a stoichiometric reaction.
- Inoue, Fumiyoshi,Kashihara, Myuto,Yadav, M. Ramu,Nakao, Yoshiaki
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supporting information
p. 13307 - 13309
(2017/10/17)
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- Nano PdAu Bimetallic Alloy as an Effective Catalyst for the Buchwald-Hartwig Reaction
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It is highly challenging but desirable to develop efficient heterogeneous catalysts for C-Cl bond activation in coupling reactions. Here, we succeeded in synthesizing bimetallic Pd-Au nanoparticles through a convenient one-pot wet chemical route. The composition and alloyed structure of the as-prepared nanoparticles were fully characterized. We have evaluated the catalytic activity of these Pd-Au alloy catalysts in Buchwald-Hartwig reactions of aryl chlorides. The excellent catalytic activity of the as-obtained Pd-Au nanoparticles indicates that exploiting the catalytic power of nano-alloy catalysts could enable effective C-Cl bond activation suitable for cross-coupling reactions.
- Chen, Zheng,Wang, Shuo,Lian, Chao,Liu, Yuxi,Wang, Dingsheng,Chen, Chen,Peng, Qing,Li, Yadong
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p. 351 - 355
(2016/05/19)
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- Solvent-Free Buchwald-Hartwig (Hetero)arylation of Anilines, Diarylamines, and Dialkylamines Mediated by Expanded-Ring N-Heterocyclic Carbene Palladium Complexes
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A highly efficient solvent-free protocol for the Buchwald-Hartwig (hetero)arylation of anilines, diarylamines, and dialkylamines mediated by the expanded-ring N-heterocyclic carbene palladium complex (THP-Dipp)Pd(cinn)Cl [THP-Dipp = 1,3-bis(2,6-diisopropylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene; cinn = cinnamyl, 3-phenylallyl] was developed. The catalytic protocol was efficient for the coupling of amines and (hetero)aryl chlorides and bromides bearing donor, acceptor, and bulky substituents.
- Topchiy, Maxim A.,Dzhevakov, Pavel B.,Rubina, Margarita S.,Morozov, Oleg S.,Asachenko, Andrey F.,Nechaev, Mikhail S.
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supporting information
p. 1908 - 1914
(2016/04/20)
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- Pd-indenyl-diphosphine: An effective catalyst for the preparation of triarylamines
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A new Buchwald-type diphosphine ligand has been developed for applications in Pd-catalyzed amination reactions towards the preparation of triarylamines. The catalyst can be used to perform the amination of a diverse array of aryl and heteroaryl chlorides.
- Yan, Meng-Qi,Yuan, Jia,Pi, Yun-Xiao,Liang, Jin-Hua,Liu, Yan,Wu, Qing-Guo,Luo, Xue,Liu, Sheng-Hua,Chen, Jian,Zhu, Xiao-Lei,Yu, Guang-Ao
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supporting information
p. 451 - 454
(2016/01/12)
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- Photochemical Synthesis of Complex Carbazoles: Evaluation of Electronic Effects in Both UV- and Visible-Light Methods in Continuous Flow
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An evaluation of both a visible-light- and UV-light-mediated synthesis of carbazoles from various triarylamines with differing electronic properties under continuous-flow conditions has been conducted. In general, triarylamines bearing electron-rich groups tend to produce higher yields than triarylamines possessing electron-withdrawing groups. The incorporation of nitrogen-based heterocycles, as well as halogen-containing arenes in carbazole skeletons, was well tolerated, and often synthetically useful complementarity was observed between the UV-light and visible-light (photoredox) methods.
- Hernandez-Perez, Augusto C.,Caron, Antoine,Collins, Shawn K.
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supporting information
p. 16673 - 16678
(2015/11/09)
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- Method for producing hydroxytriarylamine (by machine translation)
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PROBLEM TO BE SOLVED: To economically provide arylamines such as triarylamine. SOLUTION: An arylamine compound represented by formula (1) and an aryl compound having a leaving group represented by formula (2): X-Ar2-X1, are subjected to an arylamination reaction in the presence of a basic group, an alkaline metal salt and/or an alkaline earth metal salt, and an iron catalyst to thereby obtain arylamines such as triarylamines. In formula (1), Ar and Ar1are identical or different, and denote a substituted or non-substituted aryl group, and may be ring-condensed; and a denotes 1 or 2. In formula (2), X and X1are identical or different, and denote at least one leaving group selected from the group consisting of H or Br, I, CMs (mesylate), OTf (triflate) and OTs (tosylate), provided that X and X1are not simultaneously H, and have at least one leaving group; and Ar2denotes a substituted or non-substituted aryl group. COPYRIGHT: (C)2012,JPO&INPIT
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Paragraph 0034-0036
(2018/02/24)
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- Nickel-catalyzed triarylamine synthesis: Synthetic and mechanistic aspects
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An improved protocol was described for the amination of chloroarenes with diarylamines under NiCl2(PCy3)2 catalysis in the presence of a Grignard reagent as base. This method fully suits bromo-/iodoarene substrates as well, and even is expanded to certain aryl tosylates. A preliminary investigation into the mechanism suggests that this amination reaction might proceed through NiI and NiIII intermediates rather than via the usually expected Ni0-Ni II cycle.
- Li, Xin-Le,Wu, Wei,Fan, Xin-Heng,Yang, Lian-Ming
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supporting information
p. 1232 - 1236
(2014/03/21)
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- Iron-catalyzed aromatic amination for nonsymmetrical triarylamine synthesis
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Novel iron-catalyzed amination reactions of various aryl bromides have been developed for the synthesis of diaryl- and triarylamines. The key to the success of this protocol is the use of in situ generated magnesium amides in the presence of a lithium halide, which dramatically increases the product yield. The present method is simple and free of precious and expensive metals and ligands, thus providing a facile route to triarylamines, a recurrent core unit in organic electronic materials as well as pharmaceuticals.
- Hatakeyama, Takuji,Imayoshi, Ryuji,Yoshimoto, Yuya,Ghorai, Sujit K.,Jin, Masayoshi,Takaya, Hikaru,Norisuye, Kazuhiro,Sohrin, Yoshiki,Nakamura, Masaharu
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supporting information
p. 20262 - 20265
(2013/02/23)
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- Ni-catalyzed arylation of bromomagnesium diarylamides with aryl N,N-dimethylsulfamates
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The combination use of Ni(cod)2 and N,N-1,3-bis(2,6- diisopropylphenyl)-4-imidazoline-2-ylidene as a catalyst successfully gave unsymmetrical N,N-diaryl-N′,N′-diphenyl-1,1′-biphenyl-4, 4′-diamines through the arylation of bromomagnesium diarylamide with 1-(4′-diphenylamino-1,1′-biphenylyl) N,N-dimethylsulfamate. This Ni catalyst and Grignard reagents of diaryl or monoarylamides were also useful in the syntheses of various triarylamines and diarylamines from corresponding aryl N,N-dimethylsulfamates. 2012 Elsevier Ltd. All rights reserved.
- Tadaoka, Hiroshi,Yamakawa, Tetsu
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p. 5531 - 5534
(2012/11/13)
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- Construction of electrocatalytic electrodes bearing the triphenylamine nucleus covalently bound to carbon. A halogen dance in protonated aminotriphenylamines
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The triarylamine nucleus has been attached to a carbon fiber electrode by diazotization of an aminotriphenylamine followed by electrochemical reduction. The resulting electrodes can electrocatalyze the oxidation of organic substrates. In acid, 4-amino-4′,4″-dibromotriphenylamine undergoes dismutation into a mixture of amines containing from 0 to 3 bromine atoms.
- Mayers, Brian T.,Fry, Albert J.
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p. 411 - 414
(2007/10/03)
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- Palladium catalysed aryl amination reactions in supercritical carbon dioxide
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Palladium catalysed C-N bond formation in supercritical carbon dioxide has been accomplished. Carbamic acid formation is avoided in part through the use of an N-silylamine as the coupling partner. Employing a catalyst system of Pd 2dba3 (1 mol%) and 2-dicyclohexylphosphino-2′, 4′,6′-triisopropyl-1,1′-biphenyl (X-Phos) (2 mol%) enabled the catalytic amination of aryl bromides and chlorides with N-silylanilines to be realised in excellent yield. Extension of the methodology to the N-arylation of N-silyldiarylamines, N-silylazoles and N-silylsulfonamides is reported. The Royal Society of Chemistry 2005.
- Smith, Catherine J.,Tsang, Melanie W.S.,Holmes, Andrew B.,Danheiser, Rick L.,Tester, Jefferson W.
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p. 3767 - 3781
(2007/10/03)
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