- Ligand compound for copper catalyzed aryl halide coupling reaction, catalytic system and coupling reaction
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The invention provides a ligand compound capable of being used for copper catalyzed aryl halide coupling reaction, the ligand compound is a three-class compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group, and the invention also provides a catalytic system for the aryl halide coupling reaction. Thecatalytic system comprises a copper catalyst, a compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group adopted as a ligand, alkali and a solvent, and meanwhile, the invention also provides a system for the aryl halide coupling reaction adopting the catalyst system. The compound containing the 2-(substituted or non-substituted) aminopyridine nitrogen oxygen group can be used as the ligand for the copper catalyzed aryl chloride coupling reaction, and the ligand is stable under a strong alkaline condition and can well maintain catalytic activity when being used for the copper-catalyzed aryl chloride coupling reaction. In addition, the copper catalyst adopting the compound as the ligand can particularly effectively promote coupling of copper catalyzed aryl chloride and various nucleophilic reagents which are difficult to generate under conventional conditions, C-N, C-O and C-S bonds are generated, and numerous useful small molecule compounds are synthesized. Therefore, the aryl halide coupling reaction has a very good large-scale application prospect by adopting the copper catalysis system of the ligand.
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Paragraph 0086-0091; 0094-0095
(2021/05/29)
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- Porous polymeric ligand promoted copper-catalyzed C-N coupling of (hetero)aryl chlorides under visible-light irradiation
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A porous polymeric ligand (PPL) has been synthesized and complexed with copper to generate a heterogeneous catalyst (Cu@PPL) that has facilitated the efficient C-N coupling with various (hetero)aryl chlorides under mild conditions of visible-light irradiation at 80 °C (58 examples, up to 99% yields). This method could be applied to both aqueous ammonia and substituted amines, and is compatible to a variety of functional groups and heterocycles, as well as allows tandem C-N couplings with conjunctive dihalides. Furthermore, the heterogeneous characteristic of Cu@PPL has enabled a straightforward catalyst separation in multiple times of recycling with negligible catalytic efficiency loss by simple filtration, affording reaction mixtures containing less than 1 ppm of Cu residue. [Figure not available: see fulltext.]
- Wang, Erfei,Chen, Kaixuan,Chen, Yinan,Zhang, Jiawei,Lin, Xinrong,Chen, Mao
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- Green synthesis of N-(2-hydroxyethyl)anilines by the selective alkylation reaction in H2O
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Based on our previous work, a safer and more sustainable protocol for the synthesis of N-(2-Hydroxyethyl)anilines has been developed. The synthesis included the selective alkylation reaction of aniline with 2-chloroethanol in H2O, eliminating the need for any catalysts and solvents during synthesis. Comparing with our previous work, the salient features of this methodology are eco-friendliness, economic benefit, and the ease of obtaining target compounds. The selective alkylation reaction in H2O is amenable to scale-up for the synthesis of N-(2-Hydroxyethyl)anilines.
- Guo, Hui,Hao, Jia,Sun, Tingting,Wang, Zuoyao,Cao, Jian,Zhang, Guobao
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- METHODS FOR PREPARING BENZOXAZINES
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A method is provided for preparing a compound / the method comprising carrying out the following reaction: Formula (i); Formula (ii) where: R10 is hydrogen or a hydroxy protecting group; PG is an amine protecting group; and q is 1 where PG is a
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- Visible light-mediated Smiles rearrangements and annulations of non-activated aromatics
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We report the first examples of radical cation Smiles rearrangements. A series of aryloxy alkylamines underwent spontaneous reaction, with the amino group displacing theipso-alkoxy group through substitution, at ambient temperature and under photoactivation by visible light in the presence of an acridinium catalyst (5 mol%). The study was extended to 3-(2-methoxyphenyl)propan-1-amine derivatives, which lack an appropriateipsoleaving group. Here, efficient cyclisations resulted in displacement of the methoxy group and formation of tetrahydroquinolines.
- Lawson, Connor A.,Dominey, Andrew P.,Williams, Glynn D.,Murphy, John A.
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supporting information
p. 11445 - 11448
(2020/10/12)
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- CuI/2-Aminopyridine 1-Oxide Catalyzed Amination of Aryl Chlorides with Aliphatic Amines
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A class of 2-aminopyridine 1-oxides are discovered to be effective ligands for the Cu-catalyzed amination of less reactive (hetero)aryl chlorides. A wide range of functionalized (hetero)aryl chlorides reacted with various aliphatic amines to afford the desired products in good to excellent yields under the catalyst of CuI/2-aminopyridine 1-oxides. Furthermore, the catalyst system worked well for the coupling of cyclic secondary amines and N-methyl benzylamine with (hetero)aryl chlorides.
- Chen, Xiahong,He, Yongqiang,Liang, Yun,Liu, Wenjie,Wang, Deping,Xia, Xiaohong,Xu, Jiamin,Xu, Zhifeng,Zhang, Fuxing,Zhang, Xin
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supporting information
p. 7486 - 7490
(2020/10/12)
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- Oxalic amide ligands, and uses thereof in copper-catalyzed coupling reaction of aryl halides
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The present invention provides oxalic amide ligands and uses thereof in copper-catalyzed coupling reaction of aryl halides. Specifically, the present invention provides a use of a compound represented by formula I, wherein definitions of each group are described in the specification. The compound represented by formula I can be used as a ligand in copper-catalyzed coupling reaction of aryl halides for the formation of C—N, C—O and C—S bonds.
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Page/Page column 72
(2020/01/09)
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- HETEROCYCLIC CARBOXYLIC ACID AMIDE LIGAND AND APPLICATIONS THEREOF IN COPPER CATALYZED COUPLING REACTION OF ARYL HALOGENO SUBSTITUTE
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Provided are a heterocyclic carboxylic acid amide ligand and applications thereof in a copper catalyzed coupling reaction. Specifically, provided are uses of a compound represented by formula (I), definitions of radical groups being described in the specifications. The compound represented by formula (I) can be used as the ligand in the copper catalyzed coupling reaction of the aryl halogeno substitute, and is used or catalyzing the coupling reaction for forming the aryl halogeno substitute having C—N, C—O, C—S and other bonds.
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Paragraph 0259-0260
(2019/05/15)
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- Cu2O/1-(2-methylhydrazine-1-carbonyl)-isoquinoline 2-oxide catalyzed C-N cross-coupling reaction in aqueous media
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An experimentally simple, efficient, and inexpensive catalyst system was developed for the N-arylation of imidazole, indole, pyrrole, alkyl alcohol amines, and alkyl amines with aryl iodides and bromides. The reaction proceeds in water-ethanol media at 120 °C for 12 h with Cu2O as the catalyst, 1-(2-methylhydrazine-1-carbonyl)-isoquinoline 2-oxide (L2) as the ligand, NaOH as the base to generate a wide range of N-arylated products in moderate to excellent yields. Aqueous medium, ease of operation, and broad substrate scope give the process a benign environmental profile.
- Xie, Jian-Wei,Yao, Zhen-Bin,Wang, Xiao-Chuang,Zhang, Jie
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p. 3788 - 3792
(2019/06/08)
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- Straight Access to Indoles from Anilines and Ethylene Glycol by Heterogeneous Acceptorless Dehydrogenative Condensation
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The development of original strategies for the preparation of indole derivatives is a major goal in drug design. Herein, we report the first straight access to indoles from anilines and ethylene glycol by heterogeneous catalysis, based on an acceptorless dehydrogenative condensation, under noninert conditions. In order to achieve high selectivity, a combination of Pt/Al2O3 and ZnO have been found to slowly dehydrogenate ethylene glycol generating, after condensation with the amine and tautomeric equilibrium, the corresponding pyrrole-ring unsubstituted indoles.
- Llabres-Campaner, Pedro Juan,Ballesteros-Garrido, Rafael,Ballesteros, Rafael,Abarca, Belén
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supporting information
p. 521 - 526
(2018/01/01)
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- Heterogeneous borrowing hydrogen reactions with Pd/C and ZnO: Diol scope
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A borrowing hydrogen reaction with different diols was employed for the preparation of complex beta- gamma- or epsilon-amino alcohols from p-toluidine and tetrahydroquinoline with the aim of better understanding the applicability of the Pd/C ZnO heterogeneous catalyst.
- Llabres-Campaner, Pedro J.,Woodbridge-Ortega, Patricia,Ballesteros-Garrido, Rafael,Ballesteros, Rafael,Abarca, Belén
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supporting information
p. 4880 - 4882
(2017/11/29)
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- β-Amino alcohols from anilines and ethylene glycol through heterogeneous Borrowing Hydrogen reaction
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Borrowing Hydrogen (BH), also called Hydrogen Autotransfer (HA), reaction with neat ethylene glycol represents a key step in the preparation of β-amino alcohols. However, due to the stability of ethylene glycol, mono-activation has rarely been achieved. Herein, a combination of Pd/C and ZnO is reported as heterogeneous catalyst for this BH/HA reaction. This system results in an extremely air and moisture stable, and economic catalyst able to mono-functionalize ethylene glycol in water, without further activation of the diol. In this work, different diols and aromatic amines have been explored affording a new approach towards amino alcohols. This study reveals how the combination of two solid species can afford interesting catalytic properties in heterogeneous phase. ZnO activates ethylene glycol while Pd/C is the responsible of the BH/HA cycle. This catalytic system has also been found useful to dehydrogenate indoles affording indolines that undergo in situ BH/HA cycle prior to re-aromatization, representing a tandem heterogeneous process.
- Llabres-Campaner, Pedro J.,Ballesteros-Garrido, Rafael,Ballesteros, Rafael,Abarca, Belén
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supporting information
p. 5552 - 5561
(2017/08/22)
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- Room-temperature Cu-catalyzed: N -arylation of aliphatic amines in neat water
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A room-temperature and PTC-free copper-catalyzed N-arylation of aliphatic amines in neat water has been developed. Using a combination of CuI and 6,7-dihydroquinolin-8(5H)-one oxime as the catalyst and KOH as the base, a wide range of aliphatic amines are arylated with various aryl and heteroaryl halides to give the corresponding products in up to 95% yield.
- Wang, Deping,Zheng, Yanwen,Yang, Min,Zhang, Fuxing,Mao, Fangfang,Yu, Jiangxi,Xia, Xiaohong
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supporting information
p. 8009 - 8012
(2017/10/10)
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- Reaction of 1,2-difunctionalized ethanes with aryl iodides in copper-catalyzed cross-coupling: Application to synthesis of phenols
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A series of 1,2-difunctionalized ethanes, such as ethylene glycol, 2-aminoethanol, 1,2-diaminoethane, 2-dimethylaminoethanol N',N'-dimethylethane-1,2-diamine, were investigated to test the reactivity with aryl iodides in the presence of copper catalysts. Under the reaction conditions, they produce the various Cheteroatom cross-coupled products. Interestingly, ethylene glycol and 2-dimethylaminoethanol afforded mainly the phenolic compounds while the others produced different cross-coupled products. Although ethylene glycol and 2-dimethylaminoethanol resulted in the same product, their behaviors in the reaction were quite different: ethylene glycol appears to mostly act as the ligand and 2-dimethylaminoethanol appears to serve as both the ligand and reactant. This finding led to a copper-catalyzed synthesis of phenols using either ethylene glycol or 2-dimethylaminoethanol, which can be applied to a variety of aryl iodides, providing an alternative synthetic route to phenols.
- Kim, Jihye,Battsengel, Oyunsaikhan,Liu, Yajun,Chae, Junghyun
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supporting information
p. 2833 - 2840
(2016/02/05)
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- CuI/Oxalic Diamide Catalyzed Coupling Reaction of (Hetero)Aryl Chlorides and Amines
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A class of oxalic diamides are found to be effective ligands for promoting CuI-catalyzed aryl amination with less reactive (hetero)aryl chlorides. The reaction proceeds at 120 °C with K3PO4 as the base in DMSO to afford a wide range of (hetero)aryl amines in good to excellent yields. The bis(N-aryl) substituted oxalamides are superior ligands to N-aryl-N′-alkyl substituted or bis(N-alkyl) substituted oxalamides. Both the electronic nature and the steric property of the aromatic rings in ligands are important for their efficiency.
- Zhou, Wei,Fan, Mengyang,Yin, Junli,Jiang, Yongwen,Ma, Dawei
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supporting information
p. 11942 - 11945
(2015/10/06)
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- Bis-aryl urea derivatives as potent and selective LIM kinase (Limk) inhibitors
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The discovery/optimization of bis-aryl ureas as Limk inhibitors to obtain high potency and selectivity and appropriate pharmacokinetic properties through systematic SAR studies is reported. Docking studies supported the observed SAR. Optimized Limk inhibitors had high biochemical potency (IC50 400-fold), potent inhibition of cofilin phosphorylation in A7r5, PC-3, and CEM-SS T cells (IC50 1 μM), and good in vitro and in vivo pharmacokinetic properties. In the profiling against a panel of 61 kinases, compound 18b at 1 μM inhibited only Limk1 and STK16 with ≥80% inhibition. Compounds 18b and 18f were highly efficient in inhibiting cell-invasion/migration in PC-3 cells. In addition, compound 18w was demonstrated to be effective on reducing intraocular pressure (IOP) on rat eyes. Taken together, these data demonstrated that we had developed a novel class of bis-aryl urea derived potent and selective Limk inhibitors.
- Yin, Yan,Zheng, Ke,Eid, Nibal,Howard, Shannon,Jeong, Ji-Hak,Yi, Fei,Guo, Jia,Park, Chul Min,Bibian, Mathieu,Wu, Weilin,Hernandez, Pamela,Park, Hajeung,Wu, Yuntao,Luo, Jun-Li,Lograsso, Philip V.,Feng, Yangbo
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p. 1846 - 1861
(2015/04/21)
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- Triazole Derivatives, Process for Preparing the Same and Pharmaceutical Composition Comprising the Same
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The present invention refers to view body prostaglandin E 2 synthase -1 (mPGES-1) inhibitors having excellent effects of triazole derivatives, including as an active ingredient and manufacturing method thereof pharmaceutical composition is disc
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Paragraph 0083; 0084
(2016/11/24)
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- Green and efficient protocol for the synthesis of N-(2-hydroxyethyl)anilines by the alkylation reaction in ionic liquid
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A green and efficient protocol for the synthesis of N-(2-hydroxyethyl)anilines by the selective alkylation reaction in ionic liquid [BMIM]BF4 (1-butyl-3-methylimidazolium tetrafluoroborate) has been developed, eliminating the need for toxic and expensive catalysts and volatile organic solvents. The effects of the amount of ionic liquid, temperature, time, and substrate structure on the reaction were investigated. The conversion and selectivity of N-(2-hydroxyethyl)anilines obtained in ionic liquid [BMIM]BF4 are significantly increased in comparison to those traditional methods. Furthermore, the ionic liquid could be easily separated and reused at least five times. It provided a simple and efficient alternative way for the industrial synthesis of N-(2-hydroxyethyl)anilines.
- Guo, Hui,Zhuang, Yuwei,Cao, Jian,Zhang, Guobao
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p. 3368 - 3374
(2014/12/10)
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- Solvent-free copper-catalyzed N-arylation of amino alcohols and diamines with aryl halides
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A simple and mild method for the coupling of aryl halides with amino alcohols and diamines is described. The reactions can be performed under ligand-free and solvent-free conditions, and generate the products in good yield.
- Yin, Huiqing,Jin, Ming,Chen, Wei,Chen, Chen,Zheng, Likang,Wei, Ping,Han, Shiqing
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supporting information; experimental part
p. 1265 - 1270
(2012/03/27)
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- INDAZOLEPROPIONIC ACID AMIDE COMPOUND
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Disclosed is a compound which is useful in preventing and treating cardiac arrhythmia such as atrial fibrillation. A compound represented by formula (1) or a pharmaceutically acceptable salt of the same. In formula (1), ring X represents benzene or pyridine; R1 represents an optionally substituted alkyl group; R2 represents an optionally substituted aryl group, an optionally substituted heterocyclic group, an optionally substituted arylalkyl group or an optionally substituted heterocyclic group-substituted alkyl group; R3, R4, R5, R6, R7, R8 and R9 represent each hydrogen or an alkyl group, provided that R3 and R5 may be bonded to each other to form, together with the carbon atom adjacent thereto, a cycloalkyl group; and m represents 0 or 1.
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Page/Page column 35-36
(2012/02/01)
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- The reaction of primary aromatic amines with alkylene carbonates for the selective synthesis of bis-N-(2-hydroxy)alkylanilines: The catalytic effect of phosphonium-based ionic liquids
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At T ≥ 140 °C, different primary aromatic amines (pX-C 6H4NH2; X = H, OCH3, CH3, Cl) react with both ethylene- and propylene-carbonates to yield a chemoselective N-alkylation process: bis-N-(2-hydroxyalkyl)anilines [pX-C 6H4N(CH2CH(R)OH)2; R = H, CH 3] are the major products and the competitive formation of carbamates is substantially ruled out. At 140 °C, under solventless conditions, the model reaction of aniline with ethylene carbonate goes to completion by simply mixing stoichiometric amounts of the reagents. However, a class of phosphonium ionic liquids (PILs) such as tetraalkylphosphonium halides and tosylates turn out to be active organocatalysts for both aniline and other primary aromatic amines. A kinetic analysis monitored by 13C NMR spectroscopy, shows that bromide exchanged PILs are the most efficient systems, able to impart a more than 8-fold acceleration to the reaction. The reactions of propylene carbonate take place at a higher temperature than those of ethylene carbonate, and only in the presence of PIL catalysts. A mechanism based on the Lewis acidity of tetraalkylphosphonium cations and the nucleophilicity of halide anions has been proposed to account for both the reaction chemoselectivity and the function of the catalysts.
- Selva, Maurizio,Fabris, Massimo,Lucchini, Vittorio,Perosa, Alvise,Noe, Marco
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experimental part
p. 5187 - 5198
(2010/12/25)
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- Microwave-promoted mono-N-alkylation of aromatic amines in water: A new efficient and green method for an old and problematic reaction
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A greener improvement to direct mono-N-alkylation of aromatic amines by alkyl halides was achieved using microwave irradiation in water without any catalyst.
- Marzaro, Giovanni,Guiotto, Adriano,Chilin, Adriana
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supporting information; experimental part
p. 774 - 776
(2010/04/23)
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- 2-Pyridinyl β-ketones as new ligands for roomerature CuI-catalysed C-N coupling reactions
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2-Pyridinyl β-ketones were identified as new efficient ligands for CuI-catalysed N-arylation of aliphatic amines at room temperature with great selectivity and substrate scope tolerance.
- Wang, Deping,Ding, Ke
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supporting information; experimental part
p. 1891 - 1893
(2009/10/23)
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- N- versus O-arylation of aminoalcohols: Orthogonal selectivity in copper-based catalysts
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Two complementary protocols for copper-catalyzed arylation of aminoalcohols were developed. Selective N-arylation was accomplished at room temperature using 2-isobutyrylcyclohexanone (a β-diketone) as supporting ligand, while selective O-arylation require
- Shafir, Alexandr,Lichtor, Phillip A.,Buchwald, Stephen L.
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p. 3490 - 3491
(2008/01/01)
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- An Ullmann coupling of aryl iodides and amines using an air-stable diazaphospholane ligand
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(Chemical Equation Presented) A copper-based catalytic system, using an air-stable diazaphospholane as the ligand, was developed for an efficient Ullmann reaction between aryl iodides and alkyl or heterocyclic amines.
- Yang, Minghua,Liu, Fei
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p. 8969 - 8971
(2008/03/27)
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- Synthesis of β-amino alcohols from aromatic amines and alkylene carbonates using Na-Y zeolite catalyst
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A simple, efficient, and environmentally benign methodology for the synthesis of β-amino alcohols from aromatic amines and alkylene carbonates in the presence of the highly active and reusable solid base catalyst Na-Y zeolite is demonstrated. Georg Thieme Verlag Stuttgart.
- Shivarkar, Anandkumar B.,Gupte, Sunil P.,Chaudhari, Raghunath V.
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p. 1374 - 1378
(2007/10/03)
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- Mixtures of N,N-Bis-(2-hydroxyalkyl)-4-toluidin, their preparation and use
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Preparation of a mixture of two or more N,N-bis-(2-hydroxyalkyl)-4-toluidine compounds (I) comprises reaction of 4-toluidine (containing less than 0.2 wt.% of 3-toluidine) with at least 2 mol of alkylene oxide (per mol of 4-toluidine). Preparation of a mixture of two or more N,N-bis-(2-hydroxyalkyl)-4-toluidine compounds of formula (I) comprises reaction of 4-toluidine (containing less than 0.2 wt.% of 3-toluidine) with at least 2 mol of alkylene oxide of formula (II) (per mol of 4-toluidine). R 1>H or CH 3 (where the two residues of R 1> at direct adjoining carbon atoms does not simultaneously represent CH 3); and n, m : 0-11 (where the sum of n and m is at least 1). Independent claims are also included for: (1) (I) obtained by the method; and (2) a polymer product obtained by radical polymerization of polyester (preferably polyesters) in the presence of (I) as polymerization- or vulcanization accelerator. [Image].
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Page/Page column 5
(2008/06/13)
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- Alkoxide-Accelerated Smiles Rearrangements. Synthesis of N-(2-Hydroxyethyl)anilines from N-(2-Hydroxyethyl)(aryloxy)acetamides
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The first example of an alkoxide-accelerated Smiles rearrangement is reported.The rearrangement of N-(2-hydroxyethyl)(aryloxy)acetamides in dimethylformamide or tetrahydrofuran-18-crown-6 and potassium hydride produces useful yields of substituted N-(2-hydroxyethyl)anilines.
- Baker, William R.
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p. 5140 - 5143
(2007/10/02)
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