- I2/NaH2PO2-mediated deoxyamination of cyclic ethers for the synthesis of: N -aryl-substituted azacycles
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We have developed a protocol for efficient synthesis of N-aryl-substituted azacycles from aryl amines and cyclic ethers using I2/NaH2PO2 as the mediator. A diverse range of aryl amines and cyclic ethers undergo amination reaction to generate products in good to excellent yields with good functional group tolerance. This reaction can be easily scaled up to give N-aryl-substituted azacycles on a gram scale. Further chemical manipulation of the products enabled useful transformations of the quinoline ring, including bromination and acetylation. This journal is
- Chen, Tieqiao,Huang, Tianzeng,Li, Chunya,Li, Dongyang,Lin, Ying,Liu, Long,Tang, Zhi,Zhang, Jingjing
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supporting information
p. 21011 - 21014
(2021/12/04)
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- Mechanistic Insights into the FeCl3-Catalyzed Oxidative Cross-Coupling of Phenols with 2-Aminonaphthalenes
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The selective FeCl3-catalyzed oxidative cross-coupling reaction between phenols and primary, secondary, and tertiary 2-aminonaphthalene derivatives was investigated. The generality of this scalable method provides a sustainable alternative for preparing N,O-biaryl compounds that are widely used as ligands and catalysts. Based on a comprehensive kinetic investigation, a catalytic cycle involving a ternary complex that binds to both the coupling partners and the oxidant during the key oxidative coupling step is postulated. Furthermore, the studies showed that the reaction is regulated by off-cycle acid-base and ligand exchange processes.
- Vershinin, Vlada,Forkosh, Hagit,Ben-Lulu, Mor,Libman, Anna,Pappo, Doron
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- Visible-light-mediated borylation of aryl and alkyl halides with a palladium complex
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Palladium catalyzed visible-light-mediated borylation of inactivated aryl and alkyl halides is reported; the method provided high yields and excellent functional group compatibility. Furthermore, arylsilicates were synthesized selectively using dimethylphenylsilyl boronic ester via changing the reaction conditions. Finally, the possible reaction mechanism is determined through fluorescence quenching and turn on/off experiments.
- Zhao, Jia-Hui,Zhou, Zhao-Zhao,Zhang, Yue,Su, Xuan,Chen, Xi-Meng,Liang, Yong-Min
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p. 4390 - 4394
(2020/10/20)
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- Redox-Neutral β-C(sp3)-H Functionalization of Cyclic Amines via Intermolecular Hydride Transfer
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Herein, we report the first redox-neutral and transition-metal-free β-C(sp3)-H functionalization of cyclic amines via a consecutive intermolecular hydride transfer process. A series of N-aryl pyrrolidines and N-aryl 1,2,3,4-tetrahydropyridines decorated with CF3 and carboxylic ester functionalities are directly accessed in good yields from pyrrolidines and piperidines. This work pushes forward the application of the intermolecular hydride transfer strategy in one-step assembly of molecular complexity.
- Zhou, Lan,Shen, Yao-Bin,An, Xiao-De,Li, Xian-Jiang,Li, Shuai-Shuai,Liu, Qing,Xiao, Jian
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supporting information
p. 8543 - 8547
(2019/11/03)
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- Redox-neutral: Ortho -C-H amination of pinacol arylborates via palladium(ii)/norbornene catalysis for aniline synthesis
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A palladium(ii)/norbornene cooperative catalysis enabled redox-neutral ortho-C-H amination of pinacol aryl- or heteroarylborates for the synthesis of structurally diverse anilines is reported. This method is scalable, robust (tolerance of air and moisture), phosphine ligand-free, and compatible with a wide range of functionalities. These practical features make this reaction amenable for industry. A plethora of synthetically very useful halogenated anilines, which often cannot be prepared via other transition-metal-catalyzed aminations, are readily produced using this method. Particularly, the orthogonal reactivity between pinacol arylborates and aryl iodides is demonstrated. Preliminary deuterium-labeling studies reveal a redox-neutral ipso-protonation mechanism of this process, which will surely inspire the future development of this field. Overall, the exceptionally broad scope (47 examples) and reliability of this procedure, together with the wide availability of pinacol arylborates, make this chemistry a valuable addition to the existing methods for aniline synthesis.
- Chen, Shuqing,Wang, Peng,Cheng, Hong-Gang,Yang, Chihui,Zhou, Qianghui
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p. 8384 - 8389
(2019/09/30)
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- Aromatic amine compound, EphB4 kinase inhibitor and its derivatives, and preparation methods thereof
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The invention provides an aromatic amine compound, an EphB4 kinase inhibitor and its derivatives, and preparation methods thereof. Aryl boronic acid or aryl boronate and O-benzoyl hydroxylamine compounds which are used as starting raw materials are stirred and reacted in an organic solvent at 30-100 DEG C in an air atmosphere under the action of a palladium catalyst, a norbornene derivative and analkali, and separation and purification are carried out after the reaction in order to obtain the aromatic amine compound. The method has the advantages of inexpensive and readily available raw materials, no halide ion residual after the completion of the reaction, and mild reaction conditions. The invention also provides the method for synthesizing the EphB4 kinase inhibitor and its derivatives.The EphB4 kinase inhibitor and its derivatives can be synthesized from the synthesized 3,5-diminated halogenobenzene or halogenoid benzene only through a simple step.
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Paragraph 0140-0142
(2019/11/04)
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- Nucleophilic Amination of Methoxy Arenes Promoted by a Sodium Hydride/Iodide Composite
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A method for the nucleophilic amination of methoxy arenes was established by using sodium hydride (NaH) in the presence of lithium iodide (LiI). This method offers an efficient route to benzannulated nitrogen heterocycles. Mechanistic studies showed that the reaction proceeds through an unusual concerted nucleophilic aromatic substitution.
- Kaga, Atsushi,Hayashi, Hirohito,Hakamata, Hiroyuki,Oi, Miku,Uchiyama, Masanobu,Takita, Ryo,Chiba, Shunsuke
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supporting information
p. 11807 - 11811
(2017/09/20)
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- n-Butyllithium-mediated synthesis of N-aryl tertiary amines by reactions of fluoroarenes with secondary amines at room temperature
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A simple and facile method for the synthesis of aromatic tertiary amines by amination of fluoroarenes with secondary amines in the presence of n-butyllithium at room temperature was reported.
- Lin, Yingyin,Li, Meng,Ji, Xinfei,Wu, Jingjing,Cao, Song
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p. 1466 - 1472
(2017/02/18)
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- New, potentially chelating NHC ligands; synthesis, complexation studies, and preliminary catalytic evaluation
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Two new N-heterocyclic carbene (NHC) ligands bearing 2-morpholino and 2-piperidinyl naphthyl wingtips were synthesised (2-SIMorNap and 2-SIPipNap). Nuclear magnetic resonance studies, in conjunction with crystal structures and derivatisation of the NHC salts using a chiral counteranion, revealed that the ligand wingtips are oriented anti with respect to each other. From the free carbene, palladium, ruthenium and iridium complexes were prepared. NHC-iridium dicarbonyl complexes were made in order to extract the TEP values for these ligands. The study showed that these NHC ligands are more electron-donating than normal, aryl-substituted NHCs. The palladium complexes were tested in representative Suzuki-Miyaura cross-coupling reactions and compared to the state of the art systems. Ruthenium-catalysed ring-closing metathesis with these ligands was also performed. It was found that Grubbs’ 2nd generation catalyst incorporating 2-SIPipNap did not initiate at room temperature and required heating for RCM to occur.
- Ou, Arnold,Wu, Linglin,Salvador, Alvaro,Sipos, Gellert,Zhao, Guangzhen,Skelton, Brian W.,Sobolev, Alexandre N.,Dorta, Reto
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supporting information
p. 3631 - 3641
(2017/03/22)
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- Heterogeneous Rhodium-Catalyzed Aerobic Oxidative Dehydrogenative Cross-Coupling: Nonsymmetrical Biaryl Amines
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The first heterogeneously catalyzed oxidative dehydrogenative cross-coupling of aryl amines is reported herein. 2-Naphthylamine analogues were reacted with various electron-rich arenes using a heterogeneous Rh/C catalyst under mild aerobic conditions, thus affording nonsymmetrical biaryl amines in excellent yields with high selectivities. This reaction provides a mild, operationally simple, and efficient approach for the synthesis of biaryls which are important to pharmaceutical and materials chemistry. A jab-cross move: A heterogeneously catalyzed oxidative dehydrogenative cross-coupling of aryl amines is reported. Aryl amines were treated with various arenes using a heterogeneous Rh/C catalyst under mild aerobic conditions to selectively afford cross-coupled products, and provides an efficient synthetic method for the preparation of nonsymmetrical biaryl amines by oxidative C-H activation.
- Matsumoto, Kenji,Yoshida, Masahiro,Shindo, Mitsuru
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supporting information
p. 5272 - 5276
(2016/04/26)
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- N-(Pyridin-2-yl)benzamide: Efficient ligand for the nickel catalyzed Chan-Lam cross-coupling reaction
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An efficient protocol for the Chan-Lam cross-coupling reactions of arylboronic acids with aryl or alkyl amines has been developed by employing simple N-(pyridin-2-yl)benzamide ligand with Ni(OAc)2·4H2O in the presence of TMG base. The reaction proceeded well with high yields by employing various N-nucleophiles at low catalytic loadings.
- Keesara, Srinivas
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p. 6685 - 6688
(2016/01/28)
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- 6π/10π-Electrocyclization of ketene-iminium salts for the synthesis of substituted naphthylamines
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An intramolecular 6π/10π-electrocyclization from ketene-iminium salts was developed for the preparation of naphthylamines. Various substituents on the nitrogen, on the aromatic ring, and on the olefin were studied. Tricyclic skeletons were obtained in few steps and good overall yields. The electrocyclization of ketene-iminium salts has been computationally explored by means of DFT calculations and their activation barriers were compared to the parent triene as well as the corresponding dienyl allenes and dienyl ketenes. Electrocyclizations for ketene-iminium salts were shown to be highly exergonic and have much smaller barriers to activation.
- Villedieu-Percheron, Emmanuelle,Catak, Saron,Zurwerra, Didier,Staiger, Roman,Lachia, Mathilde,De Mesmaeker, Alain
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p. 2446 - 2449
(2014/05/06)
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- Direct base-assisted C-N bond formation between aryl halides and aliphatic tertiary amines under transition-metal-free conditions
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Direct base-mediated amination of aryl halides with aliphatic tertiary amines via an aryne intermediate was developed under transition-metal-free conditions. This operationally simple C-N bond-coupling protocol could tolerate a variety of functionalized aryl halides as well as several aliphatic tertiary amines. Moreover, this environmentally benign process provides a new strategy for direct C-N bond formation.
- Fang, Yang,Zheng, Yueqin,Wang, Zhiyong
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supporting information; experimental part
p. 1495 - 1498
(2012/04/17)
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- Synthesis, structural characterization, and catalytic activity of IPrNi(styrene)2 in the amination of aryl tosylates
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A novel bis-styrene IPrNi0 derivative has been synthesized from the reaction of Ni(COD)2 and free 1,3-bis(2,6-diisopropylphenyl) imidazolidene (IPr) ligand in the presence of styrene. The complex has been characterized by spectroscopic data as well as by X-ray crystallography. Its catalytic performance in the amination reaction of aryl tosylates is also reported. The catalytic reactions proceed in a very selective manner, affording moderate to high yields of cross-coupling products in short reaction times at 110 °C.
- Iglesias, Maria Jose,Blandez, Juan F.,Fructos, Manuel R.,Prieto, Auxiliadora,Alvarez, Eleuterio,Belderrain, Tomas R.,Nicasio, M. Carmen
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p. 6312 - 6316
(2012/10/30)
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- Nickel-catalyzed amination of aryl phosphates through cleaving aryl C-O bonds
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The amination of triaryl phosphates was achieved using a Ni(II)-(σ-Aryl) complex/NHC catalyst system in dioxane at 110 °C in the presence of NaH as base. Electron-neutral, -rich, and -deficient triaryl phosphates were coupled with a wider range of amine partners including cyclic and acyclic secondary amines, aliphatic primary amines, and anilines in good to excellent yields.
- Huang, Jin-Hua,Yang, Lian-Ming
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supporting information; experimental part
p. 3750 - 3753
(2011/09/14)
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- Transition-metal-free electrophilic amination between aryl grignard reagents and N-chloroamines
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In the presence of N,N,N′,N′-tetramethylethylenediamine (TMEDA) as an additive, easily prepared and handled N-chloroamines react with aryl Grignard reagents to give a variety of arylamines in good to excellent yields. Functional groups such as ester and nitrile are compatible under the reaction conditions (Figure Presented).
- Hatakeyama, Takuji,Yoshimoto, Yuya,Ghorai, Sujit K.,Nakamura, Masaharu
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supporting information; experimental part
p. 1516 - 1519
(2010/06/20)
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- Benzannulation from alkyne without metallic catalysts at room temperature to 100 °C
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(Figure presented) An efficient, novel metal-catalyst-free aminobenzannulation of 2-(prop-2-ynyl)(oxo)benzenes 1 with various dialkylamlnes 2 afforded a variety of 2-aminonaphthalenes 3 in good to excellent yields under mild reaction conditions at room temperature to 100 °C (at most).
- Jin, Tienan,Yang, Fan,Yamamoto, Yoshinori
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supporting information; experimental part
p. 388 - 390
(2010/03/04)
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- Ni0-catalyzed direct animation of anisoles involving the cleavage of carbon-oxygen bonds
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Ni0-catalyzed cross-coupling of aryl methyl ethers with amines is described. The use of an N-heterocyclic carbene as a ligand and NaOt-Bu as a base promotes the amination of anisole derivatives via the cleavage of normally unreactive aryl carbo
- Tobisu, Mamoru,Shimasaki, Toshiaki,Chatani, Naoto
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supporting information; experimental part
p. 710 - 711
(2011/04/22)
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- Nickel-catalyzed amination of aryl tosylates
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(Chemical Equation Presented) The cross-coupling of aryl tosylates with amines and anilines was accomplished by using a Ni-based catalyst system from the combination of Ni(II)-(σ-aryl) complexes/N-heterocyclic carbenes (NHCs). The feature, scope, and limitation of this reaction are disclosed.
- Gao, Cai-Yan,Yang, Lian-Ming
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p. 1624 - 1627
(2008/09/17)
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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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- (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, 35
(2010/11/25)
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- Microwave-assisted amination from aryl triflates without base and catalyst
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(Equation presented) Aryl triflates are effectively converted to the corresponding anilines under microwave irradiation in 1-methyl-2-pyridone (NMP) without base and catalyst. Aryl triflates substituted with both electron-poor and electron-rich groups give good to excellent yields. It is noteworthy that the halogenated aryl triflates can chemoselectively react with amines to afford halogenated anilines.
- Xu, Gang,Wang, Yan-Guang
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p. 985 - 987
(2007/10/03)
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- Nickel catalyzed cross-coupling and amination reactions of aryl nitriles
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Aryl nitriles have been found to participate in cross-coupling and amination reactions via nickel-catalyzed activation of the C-CN bond. With the development of these synthetically useful transformations, aryl nitriles can now be considered along with ary
- Miller, Joseph A.,Dankwardt, John W.,Penney, Jonathan M.
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p. 1643 - 1648
(2007/10/03)
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- Metal-catalyzed amination of organic sulfonates to organic amines
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A process of preparing an organic amine having at least one unsaturated group, such as an arylamine, involving contacting an unsaturated organic sulfonate, such as an aryl sulfonate, with a reactant amine, such as an alkyl or aryl amine, in the presence of a base and a transition metal catalyst under reaction conditions. The transition metal catalyst contains a Group 8 metal and a chelating ligand, for example a Group 15-substituted arylene or Group 15-substituted metallocene, such as 1,1'-bis(diphenylphosphino)-2,2'-binaphthyl or 1,1'-bis(diphenylphosphino)-ferrocene, respectively. The aryl sulfonate can be prepared from a phenol and sulfonating agent.
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- Palladium-Catalyzed Amination of Aryl Triflates and Importance of Triflate Addition Rate
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We report that a combination of DPPF (1,1-bis(diphenylphosphino)ferrocene) and Pd(dba)2 leads to the animation of aryl triflates, a reaction that allows for the conversion of phenols to arylamines. A combination of BINAP and Pd(dba)2 also catalyzes the amination of aryl triflates, but P(o-tolyl)3 complexes were not effective catalysts. In some cases, slow addition of the aryl triflate was necessary to prevent cleavage of the triflate and generation of phenol. We found that added halide, necessary in some cross-coupling chemistry of aryl sulfonates, was an unnecessary additive and even inhibited the amination chemistry.
- Louie, Janis,Driver, Michael S.,Hamann, Blake C.,Hartwig, John F.
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p. 1268 - 1273
(2007/10/03)
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- The Willgerodt-Kindler Reactions. 6. Isomerization of the Carbonyl Group in Alkanones and Cycloalkanones
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The most unusual feature of the Willgerodt-Kindler Reactions is the facile isomerization of the carbonyl function along a chain of unbranched methylene groups, or around a cycloaliphatic ring containing several connected methylene groups.We have demonstrated that the first step in the Kindler process is the formation of enamines by reaction of the carbonyl function with secondary aliphatic amines, followed by reaction of the enamine with certain sulfur-amine catalysts to form reactive heterocyclic sulfur intermediates that facilitate the elimination-readdition of the amines reversibly along the chain.It was shown that compounds of the type R2N-S-S-NR2 are effective catalysts but not compounds of the type R2N-S-NR2.Some cyclohexanone derivatives undergo aromatization, with anomalous results in certain cases.
- Carmack, Marvin,Behforouz, Mohammad,Berchtold, Glenn A.,Berkowitz, Samuel M.,Wiesler, Donald,Barone, Ralph
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p. 1305 - 1318
(2007/10/02)
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