- METHOD FOR PRODUCING ASYMMETRIC DIARYLAMINE
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PROBLEM TO BE SOLVED: To provide a production method that makes it possible to conveniently and efficiently obtain an asymmetric diarylamine that is a partial skeleton of a compound useful as organic EL hole transport materials. SOLUTION: A diarylamine (Ar1, Ar2) and a Grignard reagent are reacted to protect an NH group, and then an aryl halide (Ar3) is reacted in the presence of a nickel catalyst, thus producing an asymmetric diarylamine represented by formula (1). SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
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Paragraph 0039-0041; 0055-0057
(2021/09/01)
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- Nitrogen-containing compound, electronic element and electronic device
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The invention belongs to the technical field of organic materials, and provides a nitrogen-containing compound represented by a chemical formula 1, an electronic element and an electronic device. Thenitrogen-containing compound can improve the performance of an electronic element.
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Paragraph 0168-0172
(2021/01/29)
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- Organic compound, electronic component, comprising same and electronic device
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The invention provides an organic compound, an electronic component comprising the same and an electronic device, and belongs to the technical field of organic electroluminescence. The compound provided by the invention contains condensed rings of carbazole and fluorene, dibenzofuran or dibenzothiophene, has a rigid plane structure and high light-emitting quantum efficiency, and can improve the thermal stability and film stability of a material. According to the invention, the low triplet state energy level is effectively improved; and the compound is used for a light-emitting layer in a red light device, can effectively improve non-uniformity of charge transmission, improves the light-emitting efficiency and stability of the device, and effectively improves the performance of the device.
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Paragraph 0116; 0165-0168; 0173
(2021/07/17)
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- Organic compound and electronic component and electronic device comprising same
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The invention provides an organic compound and an electronic element and an electronic device comprising the same, and belongs to the technical field of organic electroluminescence. The structural formula of the organic compound is composed of a structure as shown in a chemical formula 1, and the organic compound has excellent photoelectric properties, can improve the luminous efficiency and the service life of the device, and can reduce the working voltage.
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Paragraph 0113-0115; 0116-0118; 0119
(2021/07/17)
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- Organic compound and electronic device and device containing the same
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The invention relates to the technical field of organic electroluminescent materials, in particular to an organic electroluminescent material 9 with 10 -9 dihydro 9 -10 -dimethyl and oxanthrene and arylamine groups, an electronic device containing the compound and a device. The organic electroluminescent device has lower driving voltage. Higher luminous efficiency and longer service life.
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Paragraph 0216-0219; 0220-0222; 0224
(2021/09/11)
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- An Improved PIII/PV=O-Catalyzed Reductive C-N Coupling of Nitroaromatics and Boronic Acids by Mechanistic Differentiation of Rate- And Product-Determining Steps
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Experimental, spectroscopic, and computational studies are reported that provide an evidence-based mechanistic description of an intermolecular reductive C-N coupling of nitroarenes and arylboronic acids catalyzed by a redox-active main-group catalyst (1,2,2,3,4,4-hexamethylphosphetane P-oxide, i.e., 1·[O]). The central observations include the following: (1) catalytic reduction of 1·[O] to PIII phosphetane 1 is kinetically fast under conditions of catalysis; (2) phosphetane 1 represents the catalytic resting state as observed by 31P NMR spectroscopy; (3) there are no long-lived nitroarene partial-reduction intermediates observable by 15N NMR spectroscopy; (4) the reaction is sensitive to solvent dielectric, performing best in moderately polar solvents (viz. cyclopentylmethyl ether); and (5) the reaction is largely insensitive with respect to common hydrosilane reductants. On the basis of the foregoing studies, new modified catalytic conditions are described that expand the reaction scope and provide for mild temperatures (T ≥ 60 °C), low catalyst loadings (≥2 mol%), and innocuous terminal reductants (polymethylhydrosiloxane). DFT calculations define a two-stage deoxygenation sequence for the reductive C-N coupling. The initial deoxygenation involves a rate-determining step that consists of a (3+1) cheletropic addition between the nitroarene substrate and phosphetane 1; energy decomposition techniques highlight the biphilic character of the phosphetane in this step. Although kinetically invisible, the second deoxygenation stage is implicated as the critical C-N product-forming event, in which a postulated oxazaphosphirane intermediate is diverted from arylnitrene dissociation toward heterolytic ring opening with the arylboronic acid; the resulting dipolar intermediate evolves by antiperiplanar 1,2-migration of the organoboron residue to nitrogen, resulting in displacement of 1·[O] and formation of the target C-N coupling product upon in situ hydrolysis. The method thus described constitutes a mechanistically well-defined and operationally robust main-group complement to the current workhorse transition-metal-based methods for catalytic intermolecular C-N coupling.
- Li, Gen,Nykaza, Trevor V.,Cooper, Julian C.,Ramirez, Antonio,Luzung, Michael R.,Radosevich, Alexander T.
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supporting information
p. 6786 - 6799
(2020/04/30)
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- Luminescent material and application thereof
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The invention discloses a novel organic compound, which has a general formula represented by the following formula (1), wherein Ar to Ar are respectively and independently selected from one of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 condensed aryl and substituted or unsubstituted C3-C30 heteroaryl, L to L are respectively and independently selectedfrom one of a single bond, a substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C6-C30 heteroarylene and substituted or unsubstituted C6-C30 fused arylene, and R to R are respectively and independently selected from one of H, a halogen atom, cyano, C1-C20 alkoxy, cyclized or uncyclized C1-C20 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 condensed aryl and substituted or unsubstituted C3-C30 heteroaryl. When the compound provided by the invention is used as a hole transport material in an OLED device, excellent device performance and stability are shown. The invention also discloses an organic light-emitting device adopting the compound with the general formula.
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Paragraph 0054-0056
(2020/06/17)
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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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- Mixed er-NHC/phosphine Pd(ii) complexes and their catalytic activity in the Buchwald-Hartwig reaction under solvent-free conditions
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A series of novel (NHC)PdCl2-PR3 complexes were synthesized and fully characterized by 1H, 13C, 31P NMR and FT-IR spectroscopy. These complexes showed high catalytic activity toward solvent-free Buchwald-Hartwig amination. Both primary and secondary amines were efficiently utilized under the same reaction conditions. The solvent-free synthesis of valuable N-aryl carbazoles and similar N-heterocyclic systems was described.
- Ageshina, Alexandra A.,Sterligov, Grigorii K.,Rzhevskiy, Sergey A.,Topchiy, Maxim A.,Chesnokov, Gleb A.,Gribanov, Pavel S.,Nechaev, Mikhail S.,Asachenko, Andrey F.,Bermeshev, Maxim V.,Melnikova, Elizaveta K.
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supporting information
p. 3447 - 3452
(2019/04/30)
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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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- 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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- Synthesis of Di(hetero)arylamines from Nitrosoarenes and Boronic Acids: A General, Mild, and Transition-Metal-Free Coupling
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The synthesis of di(hetero)arylamines by a transition-metal-free cross-coupling between nitrosoarenes and boronic acids is reported. The procedure is experimentally simple, fast, mild, and scalable and has a wide functional group tolerance, including carbonyls, nitro, halogens, free OH and NH groups. It also permits the synthesis of sterically hindered compounds.
- Roscales, Silvia,Csák?, Aurelio G.
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p. 1667 - 1671
(2018/03/23)
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- Organic Electroluminescent Materials and Devices
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The present invention includes novel borazarophenanthrene compounds, which may be used as hosts for phosphorescent emitters, charge transporters or emitters in OLEDs.
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Paragraph 0119; 0120
(2018/03/25)
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- Materials for electronic devices
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The invention relates to compounds with benzindenofluorene base bodies and to the use thereof in electronic devices, in particular in organic electroluminescent devices.
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Paragraph 0243; 0244; 0245; 0246; 0247
(2016/10/08)
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- Amine-based compounds and organic light-emitting device including the same
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Disclosed are an amine-based compound and an organic light emitting device including the same. The organic light emitting device comprises a first electrode, a second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode.
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Paragraph 0375; 0380; 0381
(2016/10/08)
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- N-substituted 2-aminobiphenylpalladium methanesulfonate precatalysts and their use in C-C and C-N cross-couplings
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A series of phosphine-ligated palladium precatalysts based on N-methyl- and N-phenyl-2-aminobiphenyl have been developed. Substitution at the nitrogen center prevents the presence of traces of aminobiphenyls that contain a free -NH2 group from contaminating cross-coupling products. These precatalysts produce N-substituted carbazoles upon activation, which cannot consume starting materials. These precatalysts were efficiently generated from 2-aminobiphenyl with minimal purification and found to be highly effective in Suzuki-Miyaura and C-N cross-coupling reactions.
- Bruno, Nicholas C.,Niljianskul, Nootaree,Buchwald, Stephen L.
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p. 4161 - 4166
(2014/05/20)
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- Pd(II)-catalyzed C(sp2)-H carbonylation of biaryl-2-amine: Synthesis of phenanthridinones
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A Pd(OAc)2-catalyzed C(sp2)-H carbonylation protocol of arenes under carbon monoxide atmosphere has been developed. The scope of the carbonylation reaction is broad and tolerates a variety of useful functional groups. This reaction provides a novel and efficient method for the synthesis of biologically and pharmaceutically significant phenanthridinones.
- Liang, Zunjun,Zhang, Jitan,Liu, Zhanxiang,Wang, Kai,Zhang, Yuhong
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p. 6519 - 6526
(2013/07/26)
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- Direct intermolecular aniline ortho- arylation via benzyne intermediates
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A method for direct, transition-metal-free ortho-arylation of anilines by aryl chlorides, bromides, fluorides, and triflates has been developed. This methodology provides the most direct approach to 2-arylanilines since no protecting or directing groups on nitrogen are required. The arylation is functional-group tolerant, with alkene, ether, trifluoromethyl, dimethylamino, carbonyl, chloro, and cyano functionalities tolerated. Phenylation of enantiopure binaphthyldiamine affords a product with >99% ee.
- Truong, Thanh,Daugulis, Olafs
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supporting information
p. 5964 - 5967
(2013/02/22)
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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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- 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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- 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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- Photoinduced cleavage of N-N bonds of aromatic hydrazines and hydrazides by visible light
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A photocatalytic system involving [Ru(bpyrz)(PFH, visible light, and air has been developed for cleavage of the N-N bonds of hydrazines and hydrazides. This catalytic system is generally effective for N,N-disubstituted hydrazine and hydrazide derivatives, including arylhydrazides, N-alkyl-N-arylhydrazines, and N,N-diarylhydrazines. The utility of this cleavage reaction has been demonstrated by synthesizing a variety of secondary aromatic amines. Georg Thieme Verlag Stuttgart ? New York.
- Zhu, Mingzhao,Zheng, Nan
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p. 2223 - 2236
(2011/09/15)
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- TRANSITION METAL CATALYTIC SYSTEMS AND METHODS FOR PREPARING ETHYLENE HOMOPOLYMERS OR COPOLYMERS OF ETHYLENE AND OLEFINS USING THE SAME
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Disclosed herein is a group IV transition metal catalyst for producing an ethylene homopolymer or an ethylene-olefin copolymers, having high catalytic activity, which includes a cyclopentadiene derivative and one or more anionic ligands having an aryl group substituted with an aryl derivative at an ortho-position thereof around a transition metal, the ligands not being crosslinked to each other, a catalyst system including the group IV transition metal catalyst and an aluminoxane cocatalyst or a boron compound cocatalyst, and a method of producing ethylene homopolymers or ethylene-olefin copolymers using the catalyst system.
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- TBDPS and Br-TBDPS protecting groups as efficient aryl group donors in Pd-catalyzed arylation of phenols and anilines
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(Chemical Equation Presented) It is shown that the TBDPS protecting group can serve as an efficient phenyl group donor for o-bromophenols via Pd-catalyzed C-H arylation followed by a routine TBAF deprotection of the resulting silacycles. Employment of the newly designed Br-TBDPS protecting group in the same sequence allows for a facile introduction of a phenyl group at the ortho position of phenols and anilines. Alternatively, switching desilylation to oxidation in the last step allows the conversion of forming silacycles into valuable o-biphenols.
- Huang, Chunhui,Gevorgyan, Vladimir
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supporting information; experimental part
p. 10844 - 10845
(2009/12/04)
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- RAPID, COST EFFECTIVE METHOD FOR SYNTHESIS OF DIARYLAMINE COMPOUNDS
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A process for forming a diarylamine compound, including reacting an aniline and an arylbromide in the presence of a palladium ligated catalyst and a base.
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Page/Page column 7-8
(2008/12/05)
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- One-step construction of carbazoles by way of the palladium-catalyzed double N-arylation reaction and its application to the total synthesis of murrastifoline-A
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The one-step construction of N-substituted carbazoles by way of the Pd-catalyzed double N-arylation reaction of primary amines with 2,2′-dibromobiphenyl is described. Aryl and aliphatic amines including tert-butylamine and a protected glucopyranosylamine were effectively transformed into the corresponding N-substituted carbazoles. The first total synthesis of murrastifoline-A, a biscarbazole alkaloid, based on this methodology is also presented.
- Kitawaki, Takafumi,Hayashi, Yoko,Ueno, Akiko,Chida, Noritaka
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p. 6792 - 6801
(2007/10/03)
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- Anionic N-fries rearrangement of N-carbamoyl diarylamines to anthranilamides. Methodology and application to acridone and pyranoacridone alkaloids
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A general alkyllithium/LDA-mediated rearrangement of N-carbamoyl diarylamines 7a-g into the anthranilamides 8a-g and 9a-g (Table 1) is presented and applied to a regioselective efficient construction of acridone (17) and pyranoacridone (18) alkaloids (Scheme 4).
- MacNeil, Stephen L.,Wilson, Brian J.,Snieckus, Victor
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p. 1133 - 1136
(2007/10/03)
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- Expanding Pd-catalyzed C-N bond-forming processes: The first amidation of aryl sulfonates, aqueous amination, and complementarity with Cu-catalyzed reactions
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The first general method for the Pd-catalyzed amination of aryl tosylates and benzenesulfonates was developed utilizing ligand 1, which belongs to a new generation of biaryl monophosphine ligands. In addition, the new catalyst system for the first time enables amidation of aryl arenesulfonates and aqueous amination protocols that do not necessitate the use of cosolvents. The substrate scope has been significantly expanded to include aryl halides containing primary amides and free carboxylic acid groups. In the case of multifunctional substrates, the Pd-catalyzed amination can provide selectivity that is complementary to the Cu-catalyzed C-N bond-forming processes. Copyright
- Huang, Xiaohua,Anderson, Kevin W.,Zim, Danilo,Jiang, Lei,Klapars, Artis,Buchwald, Stephen L.
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p. 6653 - 6655
(2007/10/03)
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- Reaction of phenylhydrazines with arenes in the presence of aluminium trichloride
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Phenylnitrenium ions are generated from phenylhydrazines by treatment with AlCl3. Reaction of a phenylnitrenium ion with arenes results in both aromatic N-substitution and C-substitution. In contrast, an N-methylphenylnitrenium ion undergoes exclusively aromatic C-substitution. Reaction of a phenylnitrenium ion with arenes present only in slight excess produces anilinated products in moderate to good yields.
- Ohwada,Nara,Sakamoto,Kikugawa
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p. 3064 - 3068
(2007/10/03)
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- N- and C-attacks on aromatics of phenylnitrenium ion generated from N-phenylhydroxylamine in the presence of trifluoroacetic acid containing polyphosphoric acid or trifluoroacetic anhydride
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A phenylnitrenium ion formed from N-phenylhydroxylamine in the presence of trifluoroacetic acid (TFA) containing polyphosphoric acid (PPA) interacts with the counterion -O2CCF3 and the unshared electron-pair of H2O, showing Hammett's ρ values -5.2 and -4.0 for N- and C-attacks on aromatics PhX (X = H, Me, Et, Ph and Cl), respectively. The ratio N-/C-attack for this nitrenium ion is lower than for the nitrenium ion interacting with only the counterion; the latter nitrenium ion is generated by the use of trifluoroacetic anhydride (TFAA) instead of PPA or by reaction of phenyl azide with aromatics in TFA. The ratio for the former nitrenium ion is affected by the aromatic substituent X:X = Me > X = Et > X = Ph > X = H > X = OMe at 20 and 50°C. The order for X = Cl is between those of X = H and X = Ph at 20°C, but highest at 50°C. The ratio is increased by higher reaction temperature and by decreased concentration of TFA. The results are demonstrated from the mechanistic viewpoint for the nitrenium ions.
- Takeuchi, Hiroshi,Taniguchi, Tomohito,Ueda, Takahiro
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p. 295 - 300
(2007/10/03)
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- Copper-catalyzed N-arylation of amines with hypervalent iodonium salts
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The copper-catalyzed N-arylation of amines with hypervalent iodonium compounds with secondary aliphatic amines, aromatic amines, azoles and amides was accomplished with catalytic CuI (10 mol%) or Cu(acac)2 (5 mol%) in the presence of Na2CO3 or K2CO3 as a base in CH2Cl2 or toluene under mild conditions.
- Kang, Suk-Ku,Lee, Sang-Ho,Lee, Duckhee
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p. 1022 - 1024
(2007/10/03)
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- THE REACTION OF ORTHO-SUBSTITUTED AROMATIC AZIDES WITH BORON TRICHLORIDE OR TRIFLUORIDE
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The reactiont of boron trichloride or trifluoride with ortho-aryl, -diazoaryl, and -arylazoaryl phenyl azides in benzene at room temperature generally gives fused azoles in high yields.Treatment of 2-nitrophenyl azide with boron trichloride mainly affords chlorinated nitroanilines, whereas with boron trifluoride it gives N-o-nitrophenylaniline.In aromatic solvents at 60 deg C in the presence of boron trifluoride-diethyl ether, 2-azidobiphenyl forms carbazole and 2-(arylamino)biphenyls, the formation of which depends greatly upon the nucleophilicity of the solvent used; however, its pseudo-first-order decomposition rate is slightly greater in benzene than in toluene or m-xylene.Under the same conditions, phenyl azide forms diarylamines.The results suggest that singlet nitrenium ions, arising from the corresponding azidetrihalogenoborane complexes by loss of molecular nitrogen, are generally the reactive intermediates.
- Spagnolo, Piero,Zanirato, Paolo
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p. 2615 - 2620
(2007/10/02)
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- N- and C-Attacks of Phenylnitrenium Ions Generated from Phenyl Azides in the Presence of Trifluoroacetic Acid and/or Trifluoromethanesulphonic Acid
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Phenylnitrenium ions were generated from phenyl azides in the presence of trifluoroacetic acid (TFA) and/or trifluoromethanesulphonic acid (TFSA).Unsubstituted phenylnitrenium ions and those with an electron-withdrawing group such as NO2 or CN undergo aromatic N-substitution, whereas those with an electron-donating group such as Me, OMe, CH2Ph, or Ph undergo C-substitution, hydrogen abstraction, and tar formation.The special character of TFA and TFSA as compared with other acids is discussed.
- Takeuchi, Hiroshi,Takano, Katsuyuki
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p. 611 - 618
(2007/10/02)
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- REACTIONS OF BORANES WITH AROMATIC AZIDES. III. A SIMPLE ROUTE TO 1,2-DIHYDRO-N-PHENYL,THIENO- AND THIENO-AZABORINES
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Some halogeno(organyl)boranes have been formed to promote fragmenatation of organic azides, through decomposition of the Lewis acid-base adducts, to give products whose structure depend on the nature of the reagents.The reactions between α,β-unsaturated ortho-thienylazides and phenylboron dichloride gave 1,2-dihydro-1-phenyl-2-chloro, thieno-, or thieno-azaborines in very good yield, via 1,6-cyclisation of the intermediate N,N-phenyldichloroborylamine resulting from a 1,2-shift of the phenyl group.New 1-phenyl-2-oxybis-(dithieno)-, and -(thieno)--azaborines were prepared by hydrolysis of the labile azaborinechloro derivatives; cyclisation to give these systems involves an intramolecular electrophilic substitution which occurs regiospecificity at the α-position in the thiophene ring.Similar reactions with 2-azidobiphenyl using wider example of chloroboranes, i.e. diphenylboron chloride, phenylboron dichloride, or boron trichloride, led to -2-amine-N-phenyl or carbazole in different ratios (9.0/0.2; 8.0/2.0; 0/10).The results can be interpreted in terms of the degree of concertedness of the three steps of the rearrangement.
- Zanirato, Paolo
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p. 285 - 294
(2007/10/02)
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- Aromatic Substitution by Phenylnitrenium and Naphthylnitrenium Ions formed from Phenyl Azide and 1-Azidonaphthalene in the Presence of Trifluoromethanesulphonic Acid
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Aromatic N-substitution by phenylnitrenium ions generated from phenyl azide in the presence of a catalytic amount of trifluoromethanesulphonic acid gave diarylamines (in especially good yield in the reaction with biphenyl or naphthalene), whereas naphthylnitrenium ions from 1-azidonaphthalene react with benzene to afford a C-substitution product, 1-amino-4-phenylnaphthalene.
- Takeuchi, Hiroshi,Takano, Katsuyuki
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p. 447 - 449
(2007/10/02)
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