- Synthesis, Structure, and Reactivity of Palladium Proazaphosphatrane Complexes Invoked in C-N Cross-Coupling
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The preparation and reactivity of elusive palladium proazaphosphatrane complexes that represent putative intermediates in C-N cross-coupling reactions are described. Variable transannulation in these compounds, as determined by X-ray crystallography, vali
- Matthews, Adrian D.,Gravalis, Gregory M.,Schley, Nathan D.,Johnson, Miles W.
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- 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; 0247-0249
(2021/03/16)
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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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- 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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- 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; 0072
(2016/12/01)
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- Feasible energy level tuning in polymer solar cells based on broad band-gap polytriphenylamine derivatives
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A series of versatile broad band-gap alternating copolymers (P1, P2, P3 and P4) based on triphenylamine (TPA) and benzofurazan derivatives, differing in the substituted groups [-OC8H17, -C8H17, -CF3, -(CF3)2] in their triphenylamine units, were designed and synthesized by Suzuki polycondensation. The relationships between the substituted groups in TPA and the highest occupied molecular orbital (HOMO) energy levels, as well as the open circuit voltages (Vocs), were investigated in detail. The HOMO levels of these four polymers decreased sequentially when the substituted groups shifted from electron-donating groups [-OC8H17, -C8H17] to electron-withdrawing groups [-CF3, -(CF3)2], which led to the successive increase in Vocs of the polymer solar cells (PSCs) based on these polymers. Through the characterization of photovoltaic performance, the highest Voc, which reached up to 1.00 V, was achieved by the polymer with bis(trifluoromenthyl) substituted group (P4), which is one of the highest Voc values based on polytriphenylamine derived polymers for PSCs. Among these polymers, the one with octyl side chain (P2) showed the best photovoltaic performance with the highest short circuit current density (Jsc) and fill factor (FF), giving a Jsc of 4.84 mA cm-2, FF of 50%, Voc of 0.80 V and power conversion efficiency (PCE) of 2.22%.
- Zhang, Bin,Chen, Guiting,Xu, Jin,Hu, Liwen,Yang, Wei
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p. 402 - 412
(2016/01/12)
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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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- 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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- 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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- Threefold cross-linked polystyrene-triphenylphosphane hybrids: Mono-P-ligating behavior and catalytic applications for aryl chloride cross-coupling and C(sp3)-H borylation
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Covalently bound polystyrene-phosphane hybrids were prepared by a method based on radical emulsion polymerization of styrenes in the presence of a tris(p-vinylphenyl)phosphane cross-linker. These hybrids favor mono-P-ligation to transition-metal complexes and are useful for challenging catalysis, such as Pd-catalyzed C-C/C-N couplings with unactivated chloroarenes and Ir- or Rh-catalyzed C(sp3)-H borylations. Copyright
- Iwai, Tomohiro,Harada, Tomoya,Hara, Kenji,Sawamura, Masaya
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supporting information
p. 12322 - 12326
(2013/12/04)
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- Clean synthesis of triarylamines: Buchwald-Hartwig reaction in water with amphiphilic resin-supported palladium complexes
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Catalytic aromatic amination was achieved in water under heterogeneous conditions by the use of palladium complexes anchored to the amphiphilic PS-PEG resin with little palladium leaching to provide a green and clean (metal-uncontaminated) protocol for the preparation of triarylamines, including the optoelectronically active N,N,N′,N′-tetraaryl-1,1′- biphenyl-4,4′-diamines (TPDs).
- Hirai, Yoshinori,Uozumi, Yasuhiro
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supporting information; experimental part
p. 1103 - 1105
(2010/06/18)
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- Heterogeneous aromatic amination of aryl halides with arylamines in water with PS-PEG resin-supported palladium complexes
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Catalytic aromatic amination is achieved in water under heterogeneous conditions by the use of immobilized palladium complexes coordinated with the amphiphilic polystyrene-poly-(ethylene glycol) resin-supported di(tert-butyl)phosphine ligand. Aromatic amination of aryl halides with diphenylamine and N,N-double arylation of anilines with bromobenzene were found to proceed in water with broad substrate tolerance to give the triarylamines in high yield with high recyclability of the polymeric catalyst beads. Very little palladium leached from the polymeric catalyst under the waterbased reaction conditions to provide a green and clean (metal-uncontaminated) protocol for the preparation of triarylamines, including the optoelectronically active N,N,N',N'-tetraaryl-1,1'-biphenyl-4,4'-diamines (TPDs).
- Hirai, Yoshinori,Uozumi, Yasuhiro
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supporting information; experimental part
p. 1788 - 1795
(2011/04/16)
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- (t-Bu)2PN=P(i-BuNCH2CH2)3N: New efficient ligand for palladium-catalyzed C-N couplings of aryl and heteroaryl bromides and chlorides and for vinyl bromides at room temperature
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(Chemical Equation Presented) By employing Pd(OAc)2, Cs 2CO3, or NaOH, and the new ligand (t-Bu) 2PN=P(i-BuNCH2CH2)3N (3a), an electronically diverse array of aryl bromides and chlorides possessing base-sensitive substituents (nitro, ester, and keto) provide coupling products with bulky aryl amines in good to excellent yields. Aryl halides possessing other functional groups including cyano, amino, trifluoromethyl, and phenol, coupled with equal ease, producing highly functionalized amines in good to excellent yields. Moreover, an aryl chloro group can be preserved in the presence of a bromo substituent under our reaction conditions. BOC-protected amines also participated efficiently. Heterocyclic bromides and chlorides underwent clean couplings with amines in excellent yields. An important strength of our protocol is the use of lower palladium loadings than those reported earlier, without compromising yields. The air-stable palladium complex (η3-cinnamyl)PdCl·(3a) (5) was also employed successfully in C-N coupling reactions while the crotyl analogue was less efficacious. The 3a/Pd(OAc)2 catalyst system promotes, for the first time, efficient coupling of vinyl bromides with a variety of amines to produce imines and enamines at room temperature.
- Reddy, Ch. Venkat,Kingston, Jesudoss V.,Verkade, John G.
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p. 3047 - 3062
(2008/09/19)
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- Synthesis of novel triphenylamine-based conjugated polyelectrolytes and their application as hole-transport layers in polymeric light-emitting diodes
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Alternating triphenylamine-based copolymers poly[N-(4- sulfonatobutyloxyphenyl)-4,4′-diphenylamine-alt-1,4-phenylene] sodium salt (PTPOBS) and poly[N-(4-sulfonatophenyl)-4,4′-diphenylamine-alt-N-(p- trifluoromethyl)phenyl-4,4′-diphenylamine] sodium salt (PTFTS) were synthesized via palladium-catalyzed Suzuki coupling reaction. These polymers are soluble only in polar solvents, such as dimethyl sulfoxide (DMSO) and a mixed solvent of methanol and N,N-dimethyl formamide (DMF), rather than in non-polar solvents such as toluene and xylene. The electrochemical and photophysical properties of the resulted copolymers were investigated. The HOMO levels of the polymers (-5.08 eV for PTPOBS and -5.24 eV for PTFTS) were close to the work function of PEDOT. The relatively high-lying LUMO levels (-2.21 eV for PTPOBS and -2.24 eV for PTFTS) revealed that they had good electron-blocking capabilities. Devices with a PTPOBS or PTFTS layer inserted between ITO or PEDOT and of red and green-emitting polymers showed lower turn-on voltages and enhanced efficiency compared with the reference devices composed of bare ITO or ITO/PEDOT as anode. These polymers can be used as an independent hole-transport/electron-blocking layer or in combination with a PEDOT layer for fabrication of multilayer devices without intermixing with the subsequent EL layer by solution processing in full-color display applications. The Royal Society of Chemistry 2006.
- Shi, Wei,Fan, Suqin,Huang, Fei,Yang, Wei,Liu, Ransheng,Cao, Yong
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p. 2387 - 2394
(2008/01/27)
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- Modular diamino- and dioxophosphine oxides and chlorides as ligands for transition-metal-catalyzed C-C and C-N couplings with aryl chlorides
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(Chemical Equation Presented) Air-stable diamino- and dioxophosphine oxides were used as ligands in palladium-catalyzed Suzuki reactions of aryl chlorides. Additionally, a diaminophosphine chloride was applied to palladium- and nickel-catalyzed C-C and C-N bond-forming reactions.
- Ackermann, Lutz,Born, Robert
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p. 2444 - 2447
(2007/10/03)
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- Scope and limitations of Pd2(dba)3/P(i-BuNCH 2CH2)3N-catalyzed Buchwald-Hartwig amination reactions of aryl chlorides
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Proazaphosphatrane ligands in combination with Pd2(dba) 3 generate highly active catalysts for Buchwald-Hartwig amination of aryl chlorides. In particular, commercially available P(i-BuNCH 2-CH2)3N is a highly general and efficient ligand, allowing the coupling of an electronically diverse set of aryl chlorides, including chloropyridines, with a wide variety of amines using 1 mol % of Pd at 100 °C. Either a 1:1 or 2:1 ratio of ligand to Pd was found to be effective. This catalyst system performs exceptionally well for sterically hindered substrates, even with only 0.25 mol % of Pd. It is shown that NaOH can also be used as the base (instead of NaO-t-Bu) allowing functionalized substrates to participate in these reactions.
- Urgaonkar, Sameer,Verkade, John G.
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p. 9135 - 9142
(2007/10/03)
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- Mechanism and Models for Copper Mediated Nucleophilic Aromatic Substitution. 2. A Single Catalytic Species from Three Different Oxidation States of Copper in an Ullmann Synthesis of Triarylamines
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Ullmann condensations of diarylamines with iodobenzenes has been investigated under homogeneous and a heterogeneous catalytic conditions with cupruos and cupric salts, as well as powered copper metal.Copper catalyzed condensation of diarylamines with iodoaromatics is relatively insensitive to substituent (for substituted iodobenzenes p=-0.25; for substituted diphenylamines p=1.09) but quite sensitive to halogen (k1/kBr.200).The first direct evidence for solution catalysis after filtration of a metal catalyzed reactions was obtained.Quantitative analysis of reaction rates, product yields, and catalyst characteristics leads to a comprehensive picture of the formation of soluble cuprous ions as the single active catalytic species under all conditions investigated.This hypothesis rationalizes many of the perplexing results which typify the literature associated with copper catalyzed nucleophilic aromatic substitution.
- Paine, Anthony James
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p. 1496 - 1502
(2007/10/02)
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