- A copper(ii) complex as an intermediate of copper(i)-catalyzed C-N cross coupling of N-phenylaniline with aryl halide by in situ ESI-MS study
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Complexes [Cu(NPh2)2]-, [Cu(NPh 2)I]- and K[Cu(phen)(NPh2) (p-tolyl)] + were observed by in situ electrospray ionization mass spectrometry (ESI-MS) analysis of the copper(i)-cata
- Tseng, Chia-Kai,Tseng, Mei-Chun,Han, Chien-Chung,Shyu, Shin-Guang
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Read Online
- DIARYL AMINE COMPOUND AND METHOD FOR PRODUCING THE SAME
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The present invention relates to a process for the preparation of diaryl amine compounds. A compound represented by chemical formula 1, a compound represented by chemical formula 2, and a synthetic reagent in a solvent, the synthetic reagent being CsF, KF, 18 - crown -6, K. 2 CO3, [TBAT] The present invention relates to a process for the preparation of diaryl amine compounds comprising a material selected from the group consisting of a (tetrabutylammonium difluorotriphenylsilicate), TBAF (tetrabutylammonium fluoride) and combinations thereof. Chemical Formula 1. Chemical Formula 2. The diaryl amine compound can be synthesized under the absence of a transition metal to be used to synthesize diaryl amine compounds having various substituents.
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Paragraph 0218; 0235-0237
(2021/03/16)
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- Design of Benzimidazolyl Phosphines Bearing AlterableP,OorP,N-Coordination: Synthesis, Characterization, and Insights into Their Reactivity
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A new series of hemilabile benzimidazolyl phosphines is reported. Entities in this ligand family can be easily assembled and prepared on a large scale via a simple one-pot procedure. X-ray crystallographic analyses show that the Pd metal center can coordinate in different fashions, where it relies on the size of the ?PR2group. With the same ligand scaffold, the ligand having a ?PCy2moiety displays better efficiency in expediting aromatic C-C bond-coupling reactions, while the ligand associated with a ?P-t-Bu2group, in contrast, promotes C-N bond-forming reactions.
- Wong, Shun Man,Choy, Pui Ying,Zhao, Qingyang,Yuen, On Ying,Yeung, Chung Chiu,So, Chau Ming,Kwong, Fuk Yee
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supporting information
p. 2265 - 2271
(2021/05/05)
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- A Tetraarylpyrrole-Based Phosphine Ligand for the Palladium-Catalyzed Amination of Aryl Chlorides
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A tetraarylpyrrole-based phosphine ligand L1 in combination with Pd(dba)2 provided a catalyst for the Buchwald-Hartwig amination reaction. A variety of amines were rapidly coupled with aryl chlorides at a Pd loading of 0.5 mol%. The selective monoarylation of aliphatic primary amines was achieved in the presence of 0.8 equiv. water. Comparison experiments were also conducted, which revealed that the catalytic activity of L1 is superior to representative phosphine ligands in the Pd-catalyzed C?N coupling of various amines. (Figure presented.).
- Sai, Masahiro
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supporting information
p. 5422 - 5428
(2021/10/08)
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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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- PHOSPHINE COMPOUND, CROSSLINKED COMPOSITION, AND MANUFACTURING METHOD OF AROMATIC AMINE COMPOUND
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PROBLEM TO BE SOLVED: To provide a phosphine compound capable of constituting a transition metal complex excellent in reaction speed and selectivity as a catalyst. SOLUTION: There is provided a phosphine compound represented by the formula (I). In the formula Ar represents each independently an aryl group which may be substituted, R1 represents each independently a linear, branched or cyclic alkyl group, R2 represents each independently a linear, branched or cyclic alkyl group, alkoxy group or aryl group which may be substituted, or neighboring 2 R2 are bound each other to form a ring, and n represents an integer of 0 to 4. SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
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Paragraph 0044-0046; 0047-0048
(2019/12/25)
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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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- METHOD FOR PRODUCING AROMATIC AMINE
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PROBLEM TO BE SOLVED: To provide a method for producing aromatic amine solving the problem that, in the case a halogen atom is selected as the well-known leaving group of a coupling reaction raw material compound, since harmful halogen waste is by-produced after reaction, waste liquid treatment is complicated and an environmental load is high and further solving the problem that, in the case a trifluoromethanesulfonyloxy group is selected as the leaving group, an environmental load upon the production of a raw material compound having a trifluoromethanesulfonyloxy group is high, and also, the production operation is complicated. SOLUTION: Provided is a method for producing an aromatic amine compound characterized in that an aromatic nitro compound and an amine compound are brought into cross coupling reaction in the presence of a metal catalyst. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPO&INPIT
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Paragraph 0047; 0049
(2018/06/13)
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- Transition-Metal-Free N-Arylation of Amines by Triarylsulfonium Triflates
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A simple and efficient method for transition-metal-free N-arylation of various amines by triarylsulfonium triflates is described. Both aliphatic and aromatic amines were smoothly converted at 80 °C in the presence of tBuOK or KOH to give the corresponding mono N-arylated products in good to high yields. The molar ratios of the reactants and the choice of bases had a big effect on the reaction. When a large excess of [Ph3S][OTf] and tBuOK were employed for primary amines under the standard conditions, the bis(N-phenyl) products were predominantly formed. This method was also applicable to the synthesis of bioactive N-phenyl amino acid derivatives. The control experiments, the deuterium labelling study, and the presence of regioisomers of N-arylated products when using 4-substituted triarylsulfonium triflates suggested that the reaction might proceed through an aryne intermediate. The present protocol demonstrated that triarylsulfonium salts are versatile arylation reagents in the construction of CAr?N bonds.
- Tian, Ze-Yu,Ming, Xiao-Xia,Teng, Han-Bing,Hu, Yu-Tian,Zhang, Cheng-Pan
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supporting information
p. 13744 - 13748
(2018/09/14)
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- Chitosan-Supported Ni particles: An Efficient Nanocatalyst for Direct Amination of Phenols
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A practical method for the direct amination of phenols using 2,4,6-trichloro-1,3,5-triazine (TCT) as an efficient promotor for the activation of phenols in the presence of an efficient and recyclable heterogeneous catalyst prepared by immobilization of nickel particles on triazole modified chitosan is described. This heterogeneous catalyst has demonstrated a promising activity for the conversion of phenolic compounds to their corresponding amine under mild conditions. Moreover, the obtained catalyst can be reused in five consecutive runs with consistent catalytic activity.
- Hajipour, Abdol R.,Abolfathi, Parisa
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- Palladium-catalyzed Selective Amination of Aryl(haloaryl)amines with 9H-Carbazole Derivatives
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Palladium-catalyzed amination of aryl(haloaryl)amines with 9H-carbazole derivatives was investigated. In the amination of (4-bromophenyl)phenylamine with 9H-carbazole by the use of Pd2(dba)3/PtBu3/NaOtBu catalyst, the main product was desired 9-[4-(phenylamino)phenyl]-9H-carbazole in 60% yield with conversion of (4-bromophenyl)phenylamine >99%, and the concomitant formation of 9-[4-[phenyl[4-(phenylamino)phenyl]amino]phenyl]-9H-carbazole (15% yield), which is the consecutive by-product, was observed. When XPhos was used instead of PtBu3, the desired product was provided in 81% yield and the consecutive by-product was suppressed to 7.7%. The yield of the desired product reached 98% by the use of tBu-XPhos. Such excellent yields of the desired product were also obtained with other 2-di-tert-butyl- or 2-di(1-adamantyl)phosphino-1,1’-biaryls. Various 9-(arylamino)aryl-9H-carbazoles could be synthesized from aryl(haloaryl)amines and 9H-carbazole derivatives in high yields by the use of tBu-XPhos. The amination of 4-bromotoluene with a mixture of diphenylamine and 9H-carbazole gave only 9-o-tolyl-9H-carbazole with tBu-XPhos, while the use of PtBu3 or XPhos afforded the mixture of 9-o-tolyl-9H-carbazole and diphenyl(o-tolyl)amine, indicating that Pd2(dba)3/tBu-XPhos/NaOtBu catalyst high selectively favors 9H-carbazole over diphenylamine as an amination substrate. (Figure presented.).
- Ohtsuka, Yuhki,Yamamoto, Tetsuya,Miyazaki, Takanori,Yamakawa, Tetsu
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p. 1007 - 1018
(2018/02/06)
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- With four hydroxy active site of three aryl amine compound and its preparation method
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The application relates to a four-hydroxy active site of three aryl amine compound of preparation method, the method to diphenylamine, to toluene as raw materials, through the halogen amino coupling, wells meyer - Harker reaction, aldol reaction, hydrogenation reaction, the reduction reaction of the ester of step to obtain the compound. The application of the preparation method uses a relatively mild reaction conditions, and has simple reaction route.
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Paragraph 0040; 0041; 0046; 0047; 0048
(2018/10/04)
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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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- Donor and acceptor substituted triphenylamines exhibiting bipolar charge-transporting and NLO properties
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Donor-acceptor type triphenylamine-based malonodinitriles were synthesized and their thermal, optical, photophysical, electrochemical and nonlinear optical properties were studied. The synthesized compounds formed glasses with the glass transition temperatures ranging from 38 to 107 °C. The ionization potentials of the samples of the compounds established by cyclic voltammetry were found to be in the range of 5.50–5.57 eV, while those estimated by photoelectron emission spectrometry ranged from 5.36 to 5.74 eV. The electron affinity values of the compounds were found to be in the range of ?3.41–?3.05 eV. The ambipolar charge-transporting properties were observed for the layers of triphenylamine-based malonodinitriles. Hole mobilities of the layers of the compounds were in the range of 10?7–10?6 cm2/V·s, while electron mobilities were by ca. two orders of magnitude higher. All the synthesized compounds had positive sign for second order hyperpolarizability.
- Gudeika, Dalius,Bundulis, Arturs,Mihailovs, Igors,Volyniuk, Dmytro,Rutkis, Martins,Grazulevicius, Juozas V.
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p. 431 - 440
(2017/02/10)
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- PdCl2(Ph3P)2/Salicylaldimine Catalyzed Diarylation of Anilines with Unactivated Aryl Chlorides
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Triphenylphosphine and salicylaldimine could be used as a mixed ligand system to obtain a high catalytic activity for palladium catalyzed diarylation of primary anilines with unactivated aryl chlorides by the synergistic effect of ligands. The activity and selectivity of the catalytic system could be improved by modifying the structure of salicylaldimine. In refluxing o-xylene, PdCl2(Ph3P)2 with 2,5-ditrifluoromethyl N-phenylsalicylaldimine as a coligand shows high efficiency for the diarylation of various anilines. The catalytic system shows good toleration for the steric hindrance of the substrates. The facile catalytic system works as well on the multiple arylation of 1,1′-biphenyl- 4,4′-diamine with aryl chlorides to afford N,N,N′,N′-tetraaryl-1,1′-biphenyl-4,4′-diamines which are important intermediates of organic light emitting diode (OLED) hole transport materials.
- Tao, Xiaochun,Li, Lei,Zhou, Yu,Qian, Xuanying,Zhao, Min,Cai, Liangzhen,Xie, Xiaomin
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supporting information
p. 1749 - 1754
(2017/10/06)
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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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- 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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- An efficient heterogeneous ligand free C-N coupling reaction catalyzed by palladium supported on magnetic nanoparticles
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The catalytic activity of palladium supported on magnetic nanoparticles in the amination coupling reaction of different nitrogen containing substrates with aryl halides was investigated. C-N bond formation was achieved in moderate to excellent yields and the catalyst could be separated by magnetic decantation.
- Rafiee, Ezzat,Ataei, Ali,Joshaghani, Mohammad
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p. 219 - 222
(2015/12/31)
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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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p. 1908 - 1914
(2016/04/20)
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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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- Synthesis of palladium complexes derived from imidazolidin-2-ylidene ligands and used for catalytic amination reactions
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N-Aryl amination and the Buchwald–Hartwig reaction are of great synthetic and industrial interest and scientists accept their usefulness and versatility for obtaining arylamines. In this study Ag–N-heterocyclic carbene complexes were used as transmetallation reagents for the synthesis of Pd–N-heterocyclic carbene complexes. The new Pd–N-heterocyclic carbene complexes were characterized using elemental analysis and 1H NMR, 13C NMR and infrared spectroscopies. The crystal structure of one, namely dichlorobis[1,3-bis(2-methylbenzyl)imidazolidin-2-yliden]palladium(II), is presented. The activity of the Pd(II) complexes in the coupling reaction of anilines or amines with bromobenzene was investigated. These complexes exhibited high catalytic activities in the direct synthesis of triarylamines and secondary amines in a single step. Copyright
- Karaca, Emine ?zge,Gürbüz, Nevin,?ahin, Onur,Büyükgüng?r, Orhan,?zdemir, ?smail
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p. 1050 - 1055
(2016/11/23)
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- A 1 - (2- [...] ) b cyclohexyl phosphine and its preparation method and application (by machine translation)
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The invention provides 1-(2-arylindenyl) dicyclohexylphosphine which takes a good catalytic effect in carbon-nitrogen coupling reaction of chlorinated or brominated aromatic hydrocarbons and diphenylamine and has the general formulas shown in the specification. According to the preparation method of 1-(2-arylindenyl) dicyclohexylphosphine, 2-aryl indene serving as a raw material reacts with n-butyllithium in the presence of high-purity nitrogen to obtain 1-(2-arylindenyl) dicyclohexylphosphine. 1-(2-arylindenyl) dicyclohexylphosphine and the preparation method and application thereof have the beneficial effects that A, B, C, D, E and F can exist in the air stably; a catalyst consisting of a compound D and palladium dibenzylacetone can catalyze reactions between various chlorinated aromatic hydrocarbons and diphenylamine and the highest yield is high up to 82%; the reactions between brominated aromatic hydrocarbons with high steric hindrance and diphenylamine can be catalyzed by the catalyst and the highest yield is high up to 85%; the reactions between chlorinated or brominated heterocyclic aromatic hydrocarbons and diphenylamine can be catalyzed by the catalyst and the highest yield is high up to 62%.
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Paragraph 0062-0067; 0071
(2016/12/01)
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- Biaryl Phosphine Based Pd(II) Amido Complexes: The Effect of Ligand Structure on Reductive Elimination
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Kinetic studies conducted under both catalytic and stoichiometric conditions were employed to investigate the reductive elimination of RuPhos (2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl) based palladium amido complexes. These complexes were found to be the resting state in Pd-catalyzed cross-coupling reactions for a range of aryl halides and diarylamines. Hammett plots demonstrated that Pd(II) amido complexes derived from electron-deficient aryl halides or electron-rich diarylamines undergo faster rates of reductive elimination. A Hammett study employing SPhos (2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl) and analogues of SPhos demonstrated that electron donation of the lower aryl group is key to the stability of the amido complex with respect to reductive elimination. The rate of reductive elimination of an amido complex based on a BrettPhos-RuPhos hybrid ligand (2-(dicyclohexylphosphino)-3,6-dimethoxy-2′,6′-diisopropoxybiphenyl) demonstrated that the presence of the 3-methoxy substituent on the "upper" ring of the ligand slows the rate of reductive elimination. These studies indicate that reductive elimination occurs readily for more nucleophilic amines such as N-alkyl anilines, N,N-dialkyl amines, and primary aliphatic amines using this class of ligands.
- Arrechea, Pedro Luis,Buchwald, Stephen L.
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supporting information
p. 12486 - 12493
(2016/10/07)
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- Structural Design Principle of Small-Molecule Organic Semiconductors for Metal-Free, Visible-Light-Promoted Photocatalysis
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Herein, we report on the structural design principle of small-molecule organic semiconductors as metal-free, pure organic and visible light-active photocatalysts. Two series of electron-donor and acceptor-type organic semiconductor molecules were synthesized to meet crucial requirements, such as 1) absorption range in the visible region, 2) sufficient photoredox potential, and 3) long lifetime of photogenerated excitons. The photocatalytic activity was demonstrated in the intermolecular C?H functionalization of electron-rich heteroaromates with malonate derivatives. A mechanistic study of the light-induced electron transport between the organic photocatalyst, substrate, and the sacrificial agent are described. With their tunable absorption range and defined energy-band structure, the small-molecule organic semiconductors could offer a new class of metal-free and visible light-active photocatalysts for chemical reactions.
- Wang, Lei,Huang, Wei,Li, Run,Gehrig, Dominik,Blom, Paul W. M.,Landfester, Katharina,Zhang, Kai A. I.
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supporting information
p. 9783 - 9787
(2016/08/10)
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- METHOD FOR COUPLING A FLUOROSULFONATE COMPOUND WITH AN AMINE COMPOUND
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The present disclosure describes a method of coupling a first compound to a second compound, the method comprising: providing the first compound having a fluorosulfonate substituent; providing the second compound comprising an amine; and reacting the first compound and the second compound in a reaction mixture, the reaction mixture including a catalyst having at least one group 10 atom, the reaction mixture under conditions effective to couple the first compound to the second compound. The present disclosure further describes a one-pot method for coupling a first compound to a second compound.
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Paragraph 0046-0047
(2016/05/02)
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- A tuned bicyclic proazaphosphatrane for catalytically enhanced n-arylation reactions with aryl chlorides
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The N-arylation of various amines with aryl chlorides proceeded in good-to-excellent yields in the presence of P[N{(p-NMe2)C6H4CH2}CH2CH2]3N (1e, a new electron-rich proazaphosphatrane ligand) and small amounts of Pd2(dba)3 (dba = dibenzylideneacetone). This catalytic system was also very effective for the synthesis of carbazoles. An efficient palladium-catalyzed N-arylation reaction of amines under mild conditions with a tuned bicyclic proazaphosphatrane has been developed.
- Kim, So Han,Kim, Min,Verkade, John G.,Kim, Youngjo
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p. 1954 - 1960
(2015/03/18)
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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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- Nickel-catalyzed cross-coupling of anisole derivatives with trimethylaluminum through the cleavage of carbonoxygen bonds
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Nickel-catalyzed cross-coupling of methoxyarenes with trimethylaluminum is described. The use of 1,3-dicyclohexylimidazol-2-ylidene as a ligand and NaO'Bu as a base promotes the methylation of anisole derivatives via the cleavage of normally unreactive aryl carbonoxygen bonds.
- Morioka, Toshifumi,Nishizawa, Akihiro,Nakamura, Keisuke,Tobisu, Mamoru,Chatani, Naoto
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supporting information
p. 1729 - 1731
(2016/02/19)
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- Compounds for Electronic Devices
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The present invention relates to compounds which are suitable for use in electronic devices, preferably organic electroluminescent devices.
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- Buchwald-Hartwig Amination of (Hetero)Aryl Tosylates Using a Well-Defined N-Heterocyclic Carbene/Palladium(II) Precatalyst
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The cross-coupling of aryl tosylates with amines and anilines was achieved by using for the first time a Pd-NHC system based on the popular Pd-PEPPSI precatalyst platform in which the anchoring imidazol-2-ylidene ligand IPr (NMe2)2 incorporates two dimethylamino groups as backbone substituents enhancing both the electronic and steric properties of the carbene. The system optimization and its application scope are disclosed.
- Zhang, Yin,Lavigne, Guy,César, Vincent
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p. 7666 - 7673
(2015/08/18)
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- Catalytic carbon-nitrogen bond-forming cross-coupling using N-trimethylsilylamines
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Carbon-nitrogen bond-forming cross-coupling reaction of haloarenes with N-trimethylsilyl (TMS)-substituted secondary and primary arylamines proceeded with the aid of a palladium catalyst and a fluoride activator. Various TMS-N(aryl)2, TMS-NH(aryl), and TMS-N(alkyl)2 reacted to give the corresponding coupled products in high yields. Multi-TMS-amine nucleophiles such as N,N-(TMS)2-aniline and N,N′-Ph2-N,N′-(TMS)2-p-phenylenediamine also participated in this C-N coupling to give multiply C-N coupled products in high yields. The novel C-N cross-coupling reaction was successfully applied to C-N bond-forming polymerization. Relative rates of the cross-coupling of p-bromotoluene with N-TMS-substituted primary and secondary amines showed that N-TMS-diphenylamine reacted faster than N-TMS-N-methylaniline or N-TMS-aniline, and N-TMS-morpholine was the least reactive, indicating that the low basicity of the nitrogen nucleophile is the key for the smooth coupling.
- Minami, Yasunori,Komiyama, Takeshi,Shimizu, Kenta,Hiyama, Tamejiro,Goto, Osamu,Ikehira, Hideyuki
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p. 1437 - 1446
(2015/11/16)
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- The compound for electronic device
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The present invention relates to compounds which are suitable for use in electronic devices, preferably organic electroluminescent devices.
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Paragraph 0112; 0113
(2016/10/08)
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- Solvent-free Buchwald-Hartwig reaction of aryl and heteroaryl halides with secondary amines
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A highly efficient solvent-free protocol for the Buchwald-Hartwig amination of (hetero)aryl halides by secondary amines was developed. The reaction is mediated by a Pd(OAc)2/RuPhos catalytic system in air. Various (hetero)aryl halides were coupled with diaryl, alkyl-aryl, and dialkylamines in good to excellent yields (51 examples, 50-99% yield). Copyright
- Topchiy, Maxim A.,Asachenko, Andrey F.,Nechaev, Mikhail S.
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p. 3319 - 3322
(2014/06/09)
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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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- Reactivity of [K3(phen)8][Cu(NPh2) 2]3 - A possible intermediate in the copper(i)-catalyzed N-arylation of N-phenylaniline
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Complex [K3(phen)8][Cu(NPh2) 2]3 (1, phen = phenanthroline) was isolated from the catalytic C-N cross coupling reaction based on the CuI-phen-tBuOK catalytic system. Complex 1 can react with 4-iodotoluene to give 4-methyl-N,N- diphenylaniline (3a) in 50% yield (based on all available NPh2 - ligands of complex 1). In addition, 1 can also work as an effective catalyst for the C-N coupling reactions under the same reaction conditions, indicating that 1 may be an effective intermediate of the catalytic system. In the presence of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), a radical scavenger, the stoichiometric reaction between complex 1 and 4-iodotoluene was significantly quenched to give a low yield of 12%. The results suggest that the radical path dominates in the reaction, with (phen)KNPh2 as the possible radical source. The structures of 1 and (phen)KNPh2 were both determined by single crystal X-ray diffraction studies.
- Tseng, Chia-Kai,Lee, Chi-Rung,Tseng, Mei-Chun,Han, Chien-Chung,Shyu, Shin-Guang
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p. 7020 - 7027
(2014/05/06)
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- Silicon-based CN cross-coupling reaction
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Palladium-catalyzed CN bond-forming cross-coupling reaction of N-trimethylsilylamines with aryl bromides and chlorides is found to proceed in the presence of a fluoride activator in 1,3-dimethyl-2-imidazolidinone (DMI), giving triarylamines in excellent yields. When aryl bromide and bis(silyl)amine were used in this reaction, double CN bondforming products were obtained in high yields. The present reaction was successfully applied to CN bond-forming polymerization.
- Shimizu, Kenta,Minami, Yasunori,Goto, Osamu,Ikehira, Hideyuki,Hiyama, Tamejiro
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supporting information
p. 438 - 440
(2014/04/17)
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- Synthesis of well-defined diphenylvinyl(cyclopropyl)phosphine-palladium complexes for the Suzuki-Miyaura reaction and Buchwald-Hartwig amination
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The well-defined diphenylvinylphosphine-palladium complex 1 and the diphenylcyclopropylphosphine-palladium complex 2 were successfully synthesized. The crystal structures of these complexes were obtained by X-ray crystallographic analysis. Both complexes were air- and moisture-stable, and could be prepared on a gram scale. These palladium complexes catalyzed the Suzuki-Miyaura reaction of aryl bromides [turnover numbers (TON) up to 196,000] and aryl chlorides (TON up to 50,000). Furthermore, complex 2 catalyzed the Buchwald-Hartwig amination of aryl chlorides and aromatic/aliphatic amines with a low catalyst loading. These complexes showed different reactivities for the coupling of 2-chloropyridine, and the origin of this difference is discussed. Copyright
- Yokoyama, Naota,Nakayama, Yuji,Nara, Hideki,Sayo, Noboru
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supporting information
p. 2083 - 2088
(2013/08/23)
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- A visible-light-mediated synthesis of carbazoles
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The photosynthetic preparation of N-aryl- and N-alkyl-bearing carbazoles utilizes continuous flow, visible light, and an in situ formed Cu-based sensitizer (see picture). The method is mild and efficient, and allows the straightforward synthesis of a variety of carbazoles with different substituents, heterocycles, and complex carbon architectures. Copyright
- Hernandez-Perez, Augusto C.,Collins, Shawn K.
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supporting information
p. 12696 - 12700
(2013/12/04)
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- Buchwald-Hartwig amination of (hetero)aryl chlorides by employing Mor-DalPhos under aqueous and solvent-free conditions
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We report on the application of the [Pd(cinnamyl)Cl]2/Mor- DalPhos catalyst system in the Buchwald-Hartwig amination of (hetero)aryl chlorides with primary or secondary amines conducted either under aqueous conditions without the use of co-solvents and/or surfactants or under solvent-free conditions (52 examples). We have established that reactions of this type can be conducted without the rigorous exclusion of air, and in the case of the solvent-free reactions, we have demonstrated that appropriately selected liquid and solid reagents can be employed successfully.
- Tardiff, Bennett J.,Stradiotto, Mark
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supporting information; experimental part
p. 3972 - 3977
(2012/08/27)
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- Simple and convenient methods for N-arylation of heterocycles and diphenylamine
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N-Arylation of NH-heterocycles and diphenylamine with various aryl halides, using a readily accessible ligand-free potassium tert-butoxide/iron(III) oxide/dimethyl sulfoxide reagent system, gives the corresponding N-aryl derivatives in 47-97% yields. Georg Thieme Verlag Stuttgart . New York.
- Alakonda, Laxhmaiah,Periasamy, Mariappan
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experimental part
p. 1063 - 1068
(2012/05/04)
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- Copper-catalyzed synthesis of triarylamines from aryl halides and arylamines
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A simple and efficient methodology for the synthesis of triphenylamines has been demonstrated using copper catalyst with a ligand and tripotassium phosphate as the base. The effect of parameters such as catalyst precursors, ligands, bases and solvents were studied and a series of triphenylamines were obtained with moderate to excellent yields in DMF. This reaction displays great functional groups compatibility in the presence of a broad range of functional groups.
- Qian, Cunwei,Xu, Shaojie,Zong, Qianshou,Fang, Dong
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p. 1881 - 1885
(2012/10/29)
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- Synthesis and properties of novel hole-transporting materials with triphenylamine units
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Two novel organic hole-transporting materials have been synthesized by combination of triphenylamines (TPA) via π-conjugated bonds using Wittig reaction. The structures were characterized by NMR, FT-IR and HRMS. The optical, electrochemical and thermal properties of the materials were studied in detail. The results show that these two compounds have blue emission, proper HOMO levels and high thermal stability. Furthermore, a quantum chemical calculation on electron distribution of the two compounds was performed, which suggests the current synthesized materials would be promising candidates for hole-transporting materials.
- Gao, Wen Zheng,Li, Xiang Gao,Wang, Shi Rong,Lv, Hai Jun
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scheme or table
p. 141 - 144
(2012/06/29)
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- Direct arylation/alkylation/magnesiation of benzyl alcohols in the presence of grignard reagents via Ni-, Fe-, or Co-catalyzed sp3 C-O Bond activation
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Direct application of benzyl alcohols (or their magnesium salts) as electrophiles in various reactions with Grignard reagents has been developed via transition metal-catalyzed sp3 C-O bond activation. Ni complex was found to be an efficient catalyst for the first direct cross coupling of benzyl alcohols with aryl/alkyl Grignard reagents, while Fe, Co, or Ni catalysts could promote the unprecedented conversion of benzyl alcohols to benzyl Grignard reagents in the presence of nhexylMgCl. These methods offer straightforward pathways to transform benzyl alcohols into a variety of functionalities.
- Yu, Da-Gang,Wang, Xin,Zhu, Ru-Yi,Luo, Shuang,Zhang, Xiao-Bo,Wang, Bi-Qin,Wang, Lei,Shi, Zhang-Jie
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supporting information
p. 14638 - 14641
(2012/11/07)
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- Pyridine-catalyzed double C-N coupling reaction of an isocyanate with two benzynes
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A pyridine-catalyzed double C-N bond cross-coupling reaction involving two benzynes with an isocyanate was carried out. The coupling reaction proceeded through a unique pathway involving the formation of an unstable carbamic acid intermediate and facile decarboxylation. Subsequent nucleophilic addition/protonation of in situ prepared amines with benzynes afforded variously substituted diaryl- and triarylamines in moderate to good yields with tolerance of a variety of functional groups. Copyright
- Lee, Yi-Hsien,Chen, Yen-Chung,Hsieh, Jen-Chieh
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supporting information; experimental part
p. 247 - 250
(2012/02/04)
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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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- Synthesis and characterization of bidentate NHC-Pd complexes and their role in amination reactions
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The new well-defined and air-stable ortho-xylyl-linked N-heterocyclic carbene (NHC) Pd complexes (2a-d) have been synthesized and characterized by elemental analysis, 1H NMR, 13C NMR, IR spectroscopy, and single crystal X-ray diffraction studies. The palladium atom in the complex 2a lies on a crystallographic mirror plane and can be described as having a square-planar coordination environment with the carbene atoms of the benzimidazole rings of the ligand occupying two coordination sites in cis positions. Two further coordination sites are occupied by chloride ligands. The benzimidazole rings are connected to each other by an ortho-xylyl bridge. The catalytic activity of these palladium complexes has been tested in the coupling reactions of various N-containing substrates with bromobenzene. A preliminary catalytic study shows that the bis(NHC)-Pd complexes are highly active in the Buchwald-Hartwig amination reaction.
- Demir, Serpil,?zdemir, Ismail,?etinkaya, Bekir,Arslan, Hakan,VanDerveer, Don
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experimental part
p. 195 - 200
(2011/03/16)
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- Chemically doped and cross-linked hole-transporting materials as an efficient anode buffer layer for polymer solar cells
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A series of cross-linkable hole-transporting materials (X-HTMs) consisting of indacenodithiophene, bithiophene, and thiophene units bookended by two triarylamine groups have been designed and synthesized to investigate their suitability as new anode buffe
- Sun, Ying,Chien, Shang-Chieh,Yip, Hin-Lap,Zhang, Yong,Chen, Kung-Shih,Zeigler, David F.,Chen, Fang-Chung,Lin, Baoping,Jen, Alex K.-Y.
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experimental part
p. 5006 - 5015
(2012/04/04)
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- Copper(I)-anilide complex [Na(phen)3][Cu(NPh2) 2]: An intermediate in the copper-catalyzed N-Arylation of N-Phenylaniline
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Complex [Na(phen)3][Cu(NPh2)2] (2), containing a linear bis(N-phenylanilide)copper(I) anion and a distorted octahedral tris(1,10-phenanthroline)sodium counter cation, has been isolated from the catalytic C-N cross-coupling reaction with the CuI/phen/tBuONa (phen=1,10-phenanthroline) catalytic system. Complex 2 can react with 4-iodotoluene to produce 4-methyl-N,N-diphenylaniline (3a) with 70.6% yield. In addition, 2 can work as an effective catalyst for Ci£N coupling under the same reaction conditions, thus indicating that 2 is the intermediate of the catalytic system. Both [Cu(NPh2) 2]- and [Cu(NPh2)I]- have been observed by in situ electron ionization mass spectrometry (ESI-MS) under catalytic reaction conditions, thus confirming that they are intermediates in the reaction. A catalytic cycle has been proposed based on these observations. The molecular structure of 2 has been determined by single-crystal X-ray diffraction analysis.
- Tseng, Chia-Kai,Lee, Chi-Rung,Han, Chien-Chung,Shyu, Shin-Guang
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experimental part
p. 2716 - 2723
(2011/04/15)
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- Palladium(II)-NHC complexes containing benzimidazole ligand as a catalyst for C-N bond formation
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The reaction of 2-(2-bromoethyl)-1,3-dioxane with 1-alkylbenzimidazole derivatives results in the formation of the new benzimidazolium salts (1). The reaction of Pd(OAc)2 with 1,3-dialkylbenzimidazolium salts (1a-c) yields palladium N-heterocyclic carbene (NHC) complexes (2a-c). All synthesized compounds were characterized by 1H NMR, 13 C NMR, IR and elemental analysis techniques which support the proposed structures. As catalysts, these new palladium complexes offer a simple and efficient methodology for the synthesis of triarylamines and secondary amines from anilines and amines and in a single step with potassium tertiary butoxide as a base.
- Dogan, Oeznur,Demir, Serpil,Oezdemir, Ismail,Cetinkaya, Bekir
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experimental part
p. 163 - 167
(2012/04/17)
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- Monovalent nickel complex bearing a bulky N-heterocyclic carbene catalyzes buchwaldhartwig amination of aryl halides under mild conditions
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Monovalent nickel complex bearing a bulky N-heterocyclic carbene (NHC) and triphenylphosphine was synthesized and demonstrated to catalyze the BuchwaldHartwig amination of aryl halides with diarylamines to form triarylamines under mild conditions.
- Nagao, Shinya,Matsumoto, Taisuke,Koga, Yuji,Matsubara, Kouki
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supporting information; experimental part
p. 1036 - 1038
(2011/12/05)
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