- 1,2-Difunctionalization of Aryl Triflates: A Direct and Modular Access to Diversely Functionalized Anilines
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ortho-Amino difunctionalization of aryl triflates has been achieved via a three-component reaction. The cascade reaction proceeds through a zincate base-mediated deprotonative formation of a reactive aryne intermediate, in situ nucleophilic addition, and coupling with electrophilic partners. This strategy leverages the advantageous reactivity of organozincate intermediates, enabling the installation of various functionalities such as amine, azide, oxygen, sulfur, halide, alkynyl, aryl, vinyl, and alkyl groups in a modular manner for the synthesis of diverse aniline skeletons.
- Cho, Seoyoung,Wang, Qiu
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supporting information
(2020/02/28)
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- Method for catalyzing nitro-arene and amine compound to be synthesized into aromatic amine compounds through palladium/imidazolium salt
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The invention discloses a method for catalyzing nitro-arene and an amine compound to be synthesized into aromatic amine through palladium/imidazolium salt. The method comprises the steps that in an organic solvent, the palladium/imidazolium salt is taken as a catalyst, the nitro-arene and the amine compound are subjected to a coupling reaction under the function of alkali, and then the aromatic amine compounds are obtained through aftertreatment. The method is simple in ligand synthesis, storage is facilitated, the price is low, the use quantity of ligands is low, the yield of the product is high, and the substrates have high applicability and are suitable for preparing diarylamine and N-alkylated arylamine. The method can be used for synthesizing a series of aromatic amine compounds, andthe aromatic amine compounds have high application value in the fields of pesticides, medicines, materials and the like.
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Paragraph 0121-0125
(2019/10/01)
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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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- 1,4-Dioxane-Tuned Catalyst-Free Methylation of Amines by CO2 and NaBH4
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A catalyst-free reductive functionalization of CO2 with amines and NaBH4 was developed. The N-methylation of amines was carried out with CO2 as a C1 building block and 1,4-dioxane as the solvent. Notably, the six-electron reduction of CO2 to form the methyl group occurred simultaneously with formation of the C?N bond to give the N-methylated amine.
- Guo, Zhiqiang,Zhang, Bo,Wei, Xuehong,Xi, Chanjuan
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p. 2296 - 2299
(2018/07/31)
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- Biphenyl sulfonic acid ligands for catalytic C-N cross coupling of aryl halides with anilines and secondary amines
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The use of two biphenyl sulfonic acid ligands for the catalytic C-N cross coupling of aryl halides with anilines, 3-aminopyridine, and secondary amines is reported. Our results represent a significant improvement compared to state of the art methods especially with regards to the removal of palladium.
- Wittel, B?rbel,Vogel, Till,Scharl, Heiko,Nerdinger, Sven,Lehnemann, Bernd,Meudt, Andreas,Snieckus, Victor
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p. 4583 - 4593
(2018/07/31)
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- Solvent-free mechanochemical Buchwald-Hartwig amination of aryl chlorides without inert gas protection
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A solvent-free Buchwald-Hartwig amination had been developed under high-speed ball-milling conditions, which afforded the desired products with moderate to high yields. The addition of sodium sulfate was found to be crucial for improving both the performance and the reproducibility. Comparative solvent-free stirring experiments implicated the importance of mechanical interaction for the transformation, and the inert gas was proved to be unnecessary for this amination.
- Shao, Qiao-Ling,Jiang, Zhi-Jiang,Su, Wei-Ke
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supporting information
p. 2277 - 2280
(2018/05/16)
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- A mechanical to urge the enters the carbon - [...] forming method (by machine translation)
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The invention discloses a mechanical to urge the enters the carbon - [...] forming method, said method comprising: in order to type 2 shown in formulae of organic amine 3 shown the chlorinated aromatic hydrocarbon as the raw material, the catalyst, ligand, in the presence of alkali and additive, the reaction is carried out by the mechanical grinding method, after the reaction mixture after the separation and purification, obtains the type 1 compound shown; in the present invention relates to mechanical grinding promotion to the chlorinated aromatic hydrocarbon as the substrate of the Buchwald - Hartwig reaction mainly adopts the organic phosphonate ligands, in the palladium catalyst under the action of the organic amine compound with the chlorinated aromatic hydrocarbon of the between the coupling, so as to obtain high yield of the target product, the majority of the reaction can be 90% or more yield. The mild reaction conditions, can be in the 1 - 2 H to complete the reaction. (by machine translation)
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Paragraph 0042; 0043; 0044; 0046; 0052
(2018/09/21)
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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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- TRANSITION-METAL-FREE N-ARYLATION OF TERTIARY AMINES USING ARYNES
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The present invention relates to transition-metal-free process for the synthesis of tertiary arylamines comprises coupling reaction between arynes and N,N-dimethyl aniline compounds in presence of 18-crown-6, KF and THF.
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Paragraph 0029; 0045
(2015/01/16)
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- Employing arynes in transition-metal-free monoarylation of aromatic tertiary amines
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The highly monoselective N-arylation of aromatic tertiary amines using a transition-metal-free approach using arynes has been developed. The reaction afforded functionalized diaryl amines in moderate to excellent yield. High levels of functional group compatibility especially with halogen containing substrates, dyes and donor-acceptor systems, and high yields of products are the notable features of the present reaction.
- Bhojgude, Sachin Suresh,Kaicharla, Trinadh,Biju, Akkattu T.
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supporting information
p. 5452 - 5455
(2013/11/19)
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- The benzyne aza-claisen reaction
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Adding an aryne to a tertiary allylamine affords oallylaniline products of an aza-Claisen rearrangement. The aryne simultaneously provides the π component for the rearrangement and the quaternization event that lowers the activation energy for the sigmatr
- Cant, Alastair A.,Bertrand, Guillaume H. V.,Henderson, Jaclyn L.,Roberts, Lee,Greaney, Michael F.
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supporting information; experimental part
p. 5199 - 5202
(2009/12/27)
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- Preparation of N-arylpiperazines and other N-aryl compounds from aryl bromides as scaffolds of bioactive compounds
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Aryl bromides are coupled with N-compounds to give the corresponding arylamines in the presence of a palladium catalyst, a suitable ligand, and a weak base. The catalysts perform well for a large number of different starting material combinations at 100-150 °C with drops of toluene or without solvent, and with low catalyst levels (0.12 mol % Pd). The low catalyst amount makes the process environment friendly.
- Romero,Harrak,Basset,Ginet,Constans,Pujol
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p. 9010 - 9016
(2007/10/03)
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- (IPr)Pd(acac)Cl: An easily synthesized, efficient, and versatile precatalyst for C-N and C-C bond formation
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A very straightforward synthesis of (IPr)Pd(acac)Cl from two commercially available starting materials, Pd(acac)2 and IPr·HCl [acac = acetylacetonate; IPr = N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene], has been developed. The resulting complex, (IPr)Pd(acac)Cl (1), has proven to be a highly active PdII precatalyst in the Buchwald-Hartwig and the α-ketone arylation reactions. A wide range of substrates has been screened, including unactivated, sterically hindered, and heterocyclic aryl chlorides.
- Marion, Nicolas,Ecarnot, Elise C.,Navarro, Oscar,Amoroso, Dino,Bell, Andrew,Nolan, Steven P.
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p. 3816 - 3821
(2007/10/03)
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- NUCLEOPHILIC HETEROCYCLIC CARBENE DERIVATIVES OF PD(ACAC)2 FOR CROSS-COUPLING REACTIONS
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Embodiments in accordance with the present invention provide for a palladium complex characterized by the general Formula (I): where A is a bidentate monoanionic ligand, NHC is a nucleophilic heterocyclic carbene, and Z is an anionic ligand. Such palladium complexes are useful in initiating cross-coupling reactions.
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Page/Page column 17, 32, 38
(2010/11/25)
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- Modified (NHC)Pd(allyl)Cl (NHC = N-heterocyclic carbene) complexes for room-temperature Suzuki-Miyaura and Buchwald-Hartwig reactions
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A series of (NHC)Pd(R-allyl)Cl complexes [NHC: IPr = N,N′-bis(2,6- diisopropylphenyl)imidazol-2-ylidene, SIPr = N,N′-bis(2,6- diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene; R = H, Me, gem-Me2, Ph] have been synthesized and fully characterized. When compared to (NHC)Pd(allyl)Cl, substitution at the terminal position of the allyl scaffold favors a more facile activation step. This translates into higher catalytic activity in the Suzuki-Miyaura and Buchwald-Hartwig reactions, allowing for the coupling of unactivated aryl chlorides at room temperature in minutes. In the Suzuki-Miyaura reaction, aryl triflates, bromides, and chlorides react with boronic acids using very low catalyst loading. In the N-aryl amination reaction, a wide range of substrates has been coupled efficiently; primary-, secondary-, alkyl-, or aryl-amines react in high yields with unactivated, neutral, and activated aryl chlorides and bromides. In both reactions, extremely hindered substrates such as tri-ortho-substituted biaryls and tetra-ortho-substituted diarylamines can be produced without loss of activity. Finally, the present catalytic system has proven to be efficient with as low as 10 parts-per-million (ppm) of precatalyst in the Buchwald-Hartwig reaction and 50 ppm in the Suzuki-Miyaura reaction.
- Marion, Nicolas,Navarro, Oscar,Mei, Jianguo,Stevens, Edwin D.,Scott, Natalie M.,Nolan, Steven P.
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p. 4101 - 4111
(2007/10/03)
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- Ruthenium-catalyzed aromatization of enediynes via highly regioselective nucleophilic additions on a π-alkyne functionality. A useful method for the synthesis of functionalized benzene derivatives
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TpRu(PPh3)(CH3CN)2PF6 (10 mol %) catalyst effected the nucleophilic addition of water, alcohols, aniline, acetylacetone, pyrroles, and dimethyl malonate to unfunctionalized enediynes under suitable conditions (100 °C, 12-24 h) and gave functionalized benzene products in good yields. In this novel cyclization, nucleophiles very regioselectively attack the internal C1′ alkyne carbon of enediynes to give benzene derivatives as a single regioisomer. Experiments with methoxy substituents exclude the possible involvement of naphthyl cations as reaction intermediates in the cyclization of (o-ethynylphenyl) alkynes. Deuterium-labeling experiments indicate that the catalytically active species is ruthenium-π-alkyne rather than ruthenium-vinylidene species. This hypothesis is further confirmed by the aromatization of o-(2′-iodoethynyl)phenyl alkynes with alcohols. We propose a nucleophilic addition/insertion mechanism for this nucleophilic aromatization on the basis of a series of experiments.
- Odedra, Arjan,Wu, Chang-Jung,Pratap, Taduri Bhanu,Huang, Chun-Wei,Ran, Ying-Fen,Liu, Rai-Shung
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p. 3406 - 3412
(2007/10/03)
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- Reactivity and Decay Pathways of Photoexcited Anilinonaphtalenes
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N-Methyl-2-anilinonaphthalene (2-MAN) is converted by light into 7-methyl-7H-benzocarbazole (7-MBC) and 5-methyl-6,7-dihydro-5H-benzocarbazole (9).The reaction takes place only in the absence of oxygen and is regioselective; i.e., the isomeric 5-methyl-5H-benzocarbazole (5-MBC) is not formed.Ring closure takes place from the excited triplet state of 2-MAN and a zwitterionic intermediate was found in flash experiments.N-Methyl-2-anilino-6-naphthalenesulfonate (2-MANS) behaves similarly.Caution should therefore be exercised if such compounds are used as fluorescence probes.N-Methyl-1-anilinonaphthalene (1-MAN) is photochemically more stable than 2-MAN.
- Grellmann, K. H.,Schmitt, U.
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p. 6267 - 6272
(2007/10/02)
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