- Visible-Light-Promoted Iron-Catalyzed N-Arylation of Dioxazolones with Arylboronic Acids
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A visible-light-promoted and simple iron salt-catalyzed N-arylation was achieved efficiently under external photosensitizer-free conditions. Arylboronic acids and bench-stable dioxazolones were used for this cross-coupling reaction. This reaction features high reactivity, wide substrate scope, good functional group tolerance, simple operation procedure, and mild reaction conditions. Preliminary mechanistic investigations were conducted to support a radical pathway. This method may contribute to shift the paradigm of iron-catalyzed C-N bond construction and nitrene transfer chemistry.
- Tang, Jing-Jing,Yu, Xiaoqiang,Yamamoto, Yoshinori,Bao, Ming
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p. 13955 - 13961
(2021/11/20)
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- Regioselective Synthesis of 2° Amides Using Visible-Light-Induced Photoredox-Catalyzed Nonaqueous Oxidative C-N Cleavage of N, N-Dibenzylanilines
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A visible-light-driven photoredox-catalyzed nonaqueous oxidative C-N cleavage of N,N-dibenzylanilines to 2° amides is reported. Further, we have applied this protocol on 2-(dibenzylamino)benzamide to afford quinazolinones with (NH4)2S2O8 as an additive. Mechanistic studies imply that the reaction might undergo in situ generation of α-amino radical to imine by C-N bond cleavage followed by the addition of superoxide ion to form amides.
- Neerathilingam, Nalladhambi,Bhargava Reddy, Mandapati,Anandhan, Ramasamy
-
supporting information
p. 15117 - 15127
(2021/10/25)
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- A practical and sustainable protocol for direct amidation of unactivated esters under transition-metal-free and solvent-free conditions
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In this paper, a NaOtBu-mediated synthesis approach was developed for direct amidation of unactivated esters with amines under transition-metal-free and solvent-free conditions, affording a series of amides in good to excellent yields at room temperature. In particular, an environmentally friendly and practical workup procedure, which circumvents the use of organic solvents and chromatography in most cases, was disclosed. Moreover, the gram-scale production of representative products3a,3wand3auwas efficiently realized by applying operationally simple, sustainable and practical procedures. Furthermore, this approach was also applicable to the synthesis of valuable molecules such as moclobemide (a powerful antidepressant), benodanil and fenfuram (two commercial agricultural fungicides). These results demonstrate that this protocol has the potential to streamline amide synthesis in industry. Meanwhile, quantitative green metrics of all the target products were evaluated, implying that the present protocol is advantageous over the reported ones in terms of environmental friendliness and sustainability. Finally, additional experiments and computational calculations were carried out to elucidate the mechanistic insight of this transformation, and one plausible mechanism was provided on the basis of these results and the related literature reports.
- Chen, Cheng,Cheng, Hua,Du, Min-Chen,Qian, Liang,Qin, Xin,Sang, Wei,Yao, Wei-Zhong,Yuan, Ye,Zhang, Rui
-
supporting information
p. 3972 - 3982
(2021/06/17)
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- Acetyl nitrate mediated conversion of methyl ketones to diverse carboxylic acid derivatives
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The development of a novel acetyl nitrate mediated oxidative conversion of methyl ketones to carboxylic acid derivatives is described. By analogy to the haloform reaction and supported by experimental and computational investigation we propose a mechanism for this transformation.
- Bernard, Josephine,Capilato, Joseph N.,Hoy, Erik P.,Mattiucci, Joseph,Pellegrinelli, Peter J.,Perez, Lark J.,Philippi, Shane,Schnorbus, Logan
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p. 5298 - 5302
(2021/06/30)
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- Iron-catalyzed oxidative amidation of acylhydrazines with amines
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A new approach for amide bond formation via a mild and efficient Iron-catalyzed cross-coupling reaction of acylhydrazines and amines using TBHP as oxidant is described. This protocol is compatible with a wide range of amines and acylhydrazines. In addition, the synthetic application of the reaction is presented.
- Wang, Yi-Jie,Zhang, Guo-Yu,Shoberu, Adedamola,Zou, Jian-Ping
-
-
- Selective hydrogenation dehalogenation method of ortho-halogenated acylaniline
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The invention discloses a selective hydrogenation dehalogenation method of copper-catalyzed ortho-halogenated acylaniline. The method comprises the following steps: by using ortho-halogenated acylaniline as a starting raw material and copper acetylacetonate/vasicine as a catalyst, adding an organic alkali, reacting in an alcoholic solution at 80-100 DEG C for 12 hours, and regioselectively catalytically hydrogenating ortho-bromine and iodine atoms. The preparation method has the characteristics of simplicity and convenience in operation, wide substrate application range, low cost, high regioselectivity and the like, and has practicability.
- -
-
Paragraph 0089-0093
(2021/01/20)
-
- Exploration of Cu-catalyzed regioselective hydrodehalogenation of o-haloanilides using EtOH as hydrogen source
-
In present work, we have explored a Cu(acac)2/vasicine-catalyzed regioselective hydrodehalogenation methodology of o-haloanilides using EtOH as hydrogen source and solvent. The catalytic system could selectively dehalogenate 2-Br and 2-I, and features regioselective, efficient and functional group tolerance.
- Li, Min-Xin,Li, Mei-Ling,Tang, Yan-Ling,Sun, Yun,Qu, Lu,Huang, Feng,Mao, Ze-Wei
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supporting information
(2021/05/03)
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- Activated charcoal supported copper nanoparticles: A readily available and inexpensive heterogeneous catalyst for the N-arylation of primary amides and lactams with aryl iodides
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A novel heterogeneous copper catalyst has been developed by supporting copper nanoparticles on activated charcoal via in situ reducing copper(II) with aqueous hydrazine as reductant. The characterization of Cu/C catalyst showed that the Cu0 nano-particles were formed on the surface of charcoal. This catalyst displayed good catalytic activities toward the N-arylation of primary amides and lactams with aryl iodides.
- Zhao, Rong,Dong, Wenwen,Teng, Jiangge,Wang, Zhiwei,Wang, Yunzhong,Yang, Jianguo,Jia, Qiang,Chu, Changhu
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supporting information
(2020/12/21)
-
- Visible-Light Carbon Nitride-Catalyzed Aerobic Cyclization of Thiobenzanilides under Ambient Air Conditions
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A metal-free heterogeneous photocatalysis has been developed for the synthesis of benzothiazoles via intramolecular C-H functionalization/C-S bond formation of thiobenzanilides by inexpensive graphitic carbon nitride (g-C3N4) under visible-light irradiation. This reaction provides access to a broad range of 2-substituted benzothiazoles in high yields under an air atmosphere at room temperature without addition of a strong base or organic oxidizing reagents. In addition, the catalyst was found to be stable and reusable after five reaction cycles.
- Bai, Jin,Yan, Sijia,Zhang, Zhuxia,Guo, Zhen,Zhou, Cong-Ying
-
supporting information
p. 4843 - 4848
(2021/06/28)
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- Decarboxylative/Oxidative Amidation of Aryl α-Ketocarboxylic Acids with Nitroarenes and Nitroso Compounds in Aqueous Medium
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The decarboxylative/oxidative amidation of aryl α-ketocarboxylic acids with 5-aryl-3-nitroisoxazole-4-carboxylates and substituted dinitrobenzenes under oxidative aqueous conditions to afford N-aryl amides is described. The reaction is suggested to proceed via a radical pathway in which a benzoyl nitroxyl radical, the key intermediate formed from reaction between nitroarene and benzoyl radical from glyoxalic acid, couples with hydroxyl radical from water to produce amide. Mechanistic insight allowed the scope of the strategy to be expanded to the synthesis of amides via reaction between aryl α-ketocarboxylic acids and nitroso compounds.
- Barak, Dinesh S.,Dahatonde, Dipak J.,Dighe, Shashikant U.,Kant, Ruchir,Batra, Sanjay
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supporting information
p. 9381 - 9385
(2020/11/30)
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- Copper-catalyzed aerobic oxidative C-C bond cleavage of simple ketones for the synthesis of amides
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A Cu-catalyzed oxidative amidation of simple ketones with amines via carbon-carbon (C-C) bond cleavage has been developed. A number of aryl and alkyl ketones could be easily converted to amides using cheap copper salt as the catalyst and O2 as the oxidant with a wide range of amines, including primary and secondary amines. This method shows a notable advantage of the broad scope for the substrate, thus providing a practical approach to amides. A plausible mechanism is proposed based on the preliminary experiments.
- Li, Ke,Liu, Wei,Liu, Yu-Feng,Yang, Guo-Ping,Zeng, Kai
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p. 6958 - 6964
(2020/10/02)
-
- Synthesis and characterization of Pd(II)–vitamin B6 complex supported on magnetic nanoparticle as an efficient and recyclable catalyst system for C–N cross coupling of amides in deep eutectic solvents
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Vitamin B6–Pd(II) immobilized onto magnetic nanoparticles have been successfully prepared and applied for C–Xcross-coupling reactions with aryl halides in green deep eutectic solvents. The results prove that the Fe3O4@vitamin B6–Pd(II) magnetic nanoparticles show high catalyst activity and good stability. It was also revealed that this complex can be recycled up to five times without any significant loss in catalytic activity.
- Bagheri, Sepideh,Pazoki, Farzane,Esfandiary, Naghmeh,Fadaei, Mohammad Mahdi,Heydari, Akbar
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- α-Imino Iridium Carbenes from Imidoyl Sulfoxonium Ylides: Application in the One-Step Synthesis of Indoles
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Imidoyl sulfoxonium ylides are presented for the first time as potential precursors to generate α-imino metal-carbene intermediates and applied in direct C-H functionalization reactions catalyzed by [Ir(cod)Cl]2 (4 mol %) to provide 2-substituted indoles (up to 70% yield) in just one step. This class of sulfur ylide is successfully obtained from imidoyl chloride and dimethylsulfoxonium methylide (23 new examples in 45-85% yield) or by imino group formation from the corresponding β-keto sulfoxonium ylides and anilines in the presence of TiCl4 as a Lewis acid (9 examples in 33-94% yield).
- Burtoloso, Antonio C. B.,Caiuby, Clarice A. D.,De Jesus, Matheus P.
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p. 7433 - 7445
(2020/06/27)
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- Clickable coupling of carboxylic acids and amines at room temperature mediated by SO2F2: A significant breakthrough for the construction of amides and peptide linkages
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The construction of amide bonds and peptide linkages is one of the most fundamental transformations in all life processes and organic synthesis. The synthesis of structurally ubiquitous amide motifs is essential in the assembly of numerous important molecules such as peptides, proteins, alkaloids, pharmaceutical agents, polymers, ligands and agrochemicals. A method of SO2F2-mediated direct clickable coupling of carboxylic acids with amines was developed for the synthesis of a broad scope of amides in a simple, mild, highly efficient, robust and practical manner (>110 examples, >90% yields in most cases). The direct click reactions of acids and amines on a gram scale are also demonstrated using an extremely easy work-up and purification process of washing with 1 M aqueous HCl to provide the desired amides in greater than 99% purity and excellent yields.
- Wang, Shi-Meng,Zhao, Chuang,Zhang, Xu,Qin, Hua-Li
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p. 4087 - 4101
(2019/04/30)
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- Electrochemical: N-acylation synthesis of amides under aqueous conditions
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An electrochemical N-acylation of carboxylic acids with amines was reported. The sustainable TBAB electrocatalysis proceeded with excellent chemoselectivity and positional selectivity, and with ample scope, allowing electrochemical N-acylation under mild reaction conditions at room temperature in water. Moreover, the synthetic utility of the current method is demonstrated by the synthesis of melatonin.
- Ke, Fang,Xu, Yiwen,Zhu, Suning,Lin, Xiaoyan,Lin, Chen,Zhou, Sunying,Su, Huimin
-
supporting information
p. 4329 - 4333
(2019/08/21)
-
- Graphene oxide-catalyzed CSp3–H activation of methylarenes in aqueous medium: A unified metal-free access to amides and benzimidazoles
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Graphene oxide (GO)-catalyzed selective synthesis of amides via CSp3–H activation of methylarenes and consequent C–N bond formation with anilines under aqueous medium has been described. Oxygen functionality allied with GO surface played a dual role both as acid catalyst and oxidizing agent to some extent. However, GO has a copious effect on the reaction, shown by a high TOF value with TBHP as co-oxidant. The decisive role of carboxylic acid functional groups on GO nanosheets in this metal-free strategy has been confirmed and was monitored by various analytic techniques viz. Fourier transform-infrared, UV–Vis, Raman and XPS. A plausible mechanism was proposed by control experiments and by the isolation of the intermediate. Over-oxidation of methylarenes was not detected, and high recyclability of the carbocatalyst with its heterogeneous behavior facilitated the isolation and purification of the desired products. We have further explored the utility of this process for the chemoselective synthesis of benzimidazoles.
- Dandia, Anshu,Mahawar, Dinesh Kumar,Sharma, Ruchi,Badgoti, Ranveer Singh,Rathore, Kuldeep S.,Parewa, Vijay
-
-
- Solvent- and transition metal-free amide synthesis from phenyl esters and aryl amines
-
A general, economical, and environmentally friendly method of amide synthesis from phenyl esters and aryl amines was developed. This new method has significant advantages compared to previously reported palladium-catalyzed approaches. The reaction is performed transition metal- and solvent-free, using a cheap and environmentally benign base, NaH. This approach enabled us to obtain target amides in high yields with high atom economy.
- Rzhevskiy, Sergey A.,Ageshina, Alexandra A.,Chesnokov, Gleb A.,Gribanov, Pavel S.,Topchiy, Maxim A.,Nechaev, Mikhail S.,Asachenko, Andrey F.
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p. 1536 - 1540
(2019/01/24)
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- Synthesis of Amides by Mild Palladium-Catalyzed Aminocarbonylation of Arylsilanes with Amines Enabled by Copper(II) Fluoride
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A general Pd-catalyzed synthesis of amides by oxidative aminocarbonylation of arylsilanes under mild conditions was accomplished for the first time. The reaction is promoted by a commercially available copper(II) fluoride, which acts as a dual silane activator and mild oxidant, enabling highly efficient aminocarbonylation of versatile arylsilanes at atmospheric CO pressure. The reaction is tolerant of a wide range of arylsilanes and various sensitive halide functional groups as well as a broad scope of amines are compatible with this oxidative process using cheap CO. A significant aspect involves the increased efficiency by the catalyst system. The reaction represents a segue into the powerful Pd-catalyzed oxidative transformations of organosilanes.
- Zhang, Jin,Hou, Yanyan,Ma, Yangmin,Szostak, Michal
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p. 338 - 345
(2019/01/10)
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- Method for synthesizing amide compound through photocatalysis in water phase
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The invention discloses a method for synthesizing an amide compound through photocatalysis in a water phase. The method comprises the following steps: putting catalysis amounts of a free radical initiator, an amine derivative, a carboxylic acid derivative, a phase transfer catalyst, an inorganic base and water into a reaction container, carrying out a reaction in a photocatalysis reaction instrument at certain power under a room temperature condition, after a certain time, carrying out extraction by using a small amount of ethyl acetate, and carrying out recrystallization, so as to obtain theamide compound, wherein the free radical initiator is eosin, methyl orange, sodium persulfate, ammonium persulfate or potassium peroxodisulfate, the phase transfer catalyst is tetrabutylammonium bromide, and the power of the photocatalytic reaction instrument is 5W. By adopting the method disclosed by the invention, toxic thionyl chloride or phosphorus oxychloride is not needed for a chlorinationreaction, water is adopted as a solvent, a novel photocatalysis method is used, and the amide compound with a high yield can be prepared through a room-temperature reaction for 2-5 hours with an incandescent light bulb of 5W, and in addition, the method is simple in aftertreatment, and low in cost and is an ideal green synthesis method of amide compounds.
- -
-
Paragraph 0018-0051
(2019/10/01)
-
- N-heterocyclic carbene palladium complex crystal, synthetic method thereof, and application thereof in preparation of amide compounds
-
The invention discloses an N-heterocyclic carbene palladium complex crystal, a synthetic method thereof and application thereof in preparation of amide compounds. The structural formula of the complexcrystal is shown in the specification, or the complex crystal is prepared from an N-heterocyclic carbene ligand, Pd(CH3CN)2Cl2 and Ag2O in acetonitrile serving as a solvent. The N-heterocyclic carbene palladium complex crystal is relatively stable, wherein the raw materials used in the synthesis method are cheap and easy to obtain, so that the synthetic method is simple, convenient and easy to implement is simple in post-treamtent and is high in yield; and the N-heterocyclic carbene palladium complex crystal is used for catalyzing carbonylation carbon-nitrogen bond coupling reaction to prepare amide compounds and is high in catalytic activity, easy to operate and high in atom economy.
- -
-
Paragraph 0029-0032; 0055-0058
(2019/12/02)
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- Synthesis of amides from acid chlorides and amines in the bio-based solvent Cyrene
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Cyrene as a bio-alternative dipolar aprotic solvent: a waste minimizing and molar efficient protocol for the synthesis of amides from acid chlorides and primary amines in the bio-available solvent Cyrene is disclosed. This protocol removed the use of toxic solvents, such as dimethylformamide and dichloromethane. A simple aqueous work-up procedure for the removal of the high boiling solvent Cyrene resulted in up to a 55-fold increase in molar efficiency (Mol E.%) versus standard operating procedures. In order to rapidly compare the molar efficiency of this process against other methodologies an Excel based Mol. E% calculator was developed that automates many of the calculations. An investigation into the hydration of Cyrene found that it readily hydrates to form a geminal diol in the presence of water and that this process is exothermic.
- Bousfield, Thomas W.,Pearce, Katharine P. R.,Nyamini, Simbarashe B.,Angelis-Dimakis, Athanasios,Camp, Jason E.
-
supporting information
p. 3675 - 3681
(2019/07/09)
-
- Exogenous Photosensitizer-, Metal-, and Base-Free Visible-Light-Promoted C-H Thiolation via Reverse Hydrogen Atom Transfer
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Visible-light-driven, intramolecular C(sp2)-H thiolation has been achieved without addition of a photosensitizer, metal catalyst, or base. This reaction induces the cyclization of thiobenzanilides to benzothiazoles. The substrate absorbs visible light, and its excited state undergoes a reverse hydrogen-atom transfer (RHAT) with 2,2,6,6-tetramethylpiperidine N-oxyl to form a sulfur radical. The addition of the sulfur radical to the benzene ring gives an aryl radical, which then rearomatizes to benzothiazole via RHAT.
- Xu, Ze-Ming,Li, Hong-Xi,Young, David James,Zhu, Da-Liang,Li, Hai-Yan,Lang, Jian-Ping
-
supporting information
p. 237 - 241
(2019/01/10)
-
- Synthesis of Secondary Amides through the Palladium(II)-Catalyzed Aminocarbonylation of Arylboronic Acids with Amines or Hydrazines and Carbon Dioxide
-
A new Pd-catalyzed aminocarbonylation of arylboronic acids with amines or phenylhydrazines has been developed. Various secondary amides were produced from readily available substrates and cheap common metal catalysts in a CO atmosphere (balloon). Remarkably, we presents the first example of aminocarbonylations between arylboronic acids and phenylhydrazines.
- Zhang, Jin,Ma, Yuqiang,Ma, Yangmin
-
supporting information
p. 1720 - 1725
(2018/04/24)
-
- Method for synthesizing N-aryl aromatic amide by adopting aromatic hydrazine
-
The invention discloses a method for synthesizing N-aryl aromatic amide by adopting aromatic hydrazine. The method includes that arylboronic acid, the aromatic hydrazine, a primary catalyst and an auxiliary catalyst are added in a solvent, the N-aryl aromatic amide as is indicated in the formula III is obtained by performing separation and purification after heating reflux reaction, and CO is fedto a reaction to enable pressure of the reaction system to be 0.1-5MPa during reaction. The method is concise and efficient, phenylhydrazine is substituted, organic boronic acid and CO which are stable in air and easy to obtain are taken as raw materials, metal palladium is taken as the primary catalyst, copper or iron is taken as the auxiliary catalyst, and the N-aryl aromatic amide is synthesized efficiently under mild reaction conditions.
- -
-
Paragraph 0069-0072
(2018/03/26)
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- Copper(II)-mediated, carbon degradation-based amidation of phenylacetic acids toward N -substituted benzamides
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The unprecedented synthesis of N-aryl substituted benzamides via the assembly of primary amines and phenylacetic acids has been developed in the presence of copper(ii) acetate. This tandem transformation involving carbon-carbon bond cleavage provides a complementary tool with particular application in the synthesis of secondary benzamides.
- Deng, Leiling,Huang, Bin,Liu, Yunyun
-
supporting information
p. 1552 - 1556
(2018/03/08)
-
- Copper-catalyzed synthesis of benzanilides from lignin model substrates 2-phenoxyacetophenones under an air atmosphere
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The synthesis of chemicals from biomass-derived compounds is an interesting and challenging topic. In this work, using the lignin-derived 2-phenoxyacetophenones as the feedstock we present a novel approach for the synthesis of benzanilides via the reaction of 2-phenoxyacetophenones with anilines catalyzed by CuCl2 in DMSO at 120 °C under an air atmosphere. This approach has wide scope for 2-phenoxyacetophenones and anilines, and various benzanilides accompanied by the corresponding phenols could be obtained in high yields via changing the 2-phenoxyacetophenones and anilines. The reaction mechanism study indicated that the oxidative cleavage of the C-C bond in 2-phenoxyacetophenones and the formation of a C-N bond occurred simultaneously in the reaction process, resulting in the formation of benzanilides together with phenols.
- Liu, Xinwei,Zhang, Hongye,Wu, Cailing,Chen, Yu,Yu, Bo,Liu, Zhimin,Liu, Zhenghui
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p. 1223 - 1227
(2018/02/06)
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- Pd-Catalyzed Oxidation of Aldimines to Amides
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Methods for the synthesis of amides via the direct oxidation of imines are rarely reported. Here we report an efficient method for Pd-catalyzed oxidation of imines to amide derivatives by the use of cheap aqueous tert -butyl hydroperoxide as an oxidant through a Wacker-type reaction. This method is practically convenient and displays high functional group tolerance, allowing a variety of imines to transform into the corresponding amide derivatives in moderate to good yields.
- Gao, Shanshan,Ma, Yaorui,Chen, Weidong,Luo, Junfei
-
supporting information
p. 2191 - 2194
(2018/10/02)
-
- Photocatalytic benzene and benzene derivative direct hydroxylation or amination method
-
The invention discloses a photocatalytic benzene and benzene derivative direct hydroxylation or amination method. The method is characterized by comprising the following steps: (1) adding a photo-sensitizer and a cobalt catalyst into a solvent to obtain a solution (A); (2) adding benzene (or benzene derivatives), water, ammonia gas, and amide derivatives (or sulfonamide derivatives) into the solution (A) to obtain a solution (B); and (3) in a N2 (or Ar) environment, radiating the solution (B) by a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, or an LED lamp to obtain phenols or amines and H2. For the first time, a photo-sensitizer and a cobalt catalyst are combined and applied to photocatalytic hydroxylation and amination of benzene. The conditions of the method are mild, light is taken as the driving energy, no oxidant is added, the only byproduct is H2, and the whole process is green, concise, and efficient. High selective benzene one-step hydroxylation to generate phenol or high selective phenol/benzene one-step amination to generate aniline is realized, and the method can be applied to the production of phenol and aniline.
- -
-
Paragraph 0154-0155
(2017/11/29)
-
- Ligand- and Solvent-Tuned Chemoselective Carbonylation of Bromoaryl Triflates
-
The palladium-catalyzed chemoselective carbonylation of bromoaryl triflates is reported. The selective C?Br bond versus C?OTf (OTf=triflate) bond functionalization can be remarkably tuned by the combination of the ligand [4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos) vs. 1,1′-bis(diphenylphosphino)ferrocene (DPPF)] and the solvent (toluene vs. DMSO). The respective ligand and solvent effects are rationalized by DFT calculations. In contrast, the monodentate ligands BuPAd2 and tBu3P prefer the selective C?Br bond activation and are solvent insensitive.
- Shen, Chaoren,Wei, Zhihong,Jiao, Haijun,Wu, Xiao-Feng
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p. 13369 - 1337
(2017/09/06)
-
- Synthesis of N -Aryl Amides by Ligand-Free Copper-Catalyzed ipso -Amidation of Arylboronic Acids with Nitriles
-
A facile copper-catalyzed ipso-amidation of arylboronic acids with nitriles has been developed. The method provides a highly efficient and economical synthesis of N-aryl amides with a broad substrate scope.
- Qiao, Yan,Li, Gaoqiang,Liu, Sha,Yangkai, Yujie,Tu, Jingxuan,Xu, Feng
-
supporting information
p. 1834 - 1838
(2017/04/06)
-
- Organic magnesium-lithium bimetallic compound, preparation method and applications thereof
-
The present invention provides an organic magnesium-lithium bimetallic compound represented by the following structure formula, wherein lithium diisopropylamide and a 2-tert-butylaminomethylpyrrole ligand are subjected to a lithiation reaction, n-butyl magnesium and TMEDA are added to the reaction product, and a reaction is further performed to obtain the organic magnesium-lithium bimetallic compound. According to the present invention, with the application of the organic magnesium-lithium bimetallic compound as the catalyst to catalyze the amidation reaction of aromatic aldehyde and aromatic amine, the high catalytic activity is provided. The structure formula of the organic magnesium-lithium bimetallic compound is defined in the specification.
- -
-
Paragraph 0024-0025
(2017/09/01)
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- Peroxide-mediated direct synthesis of amides from aroyl surrogates
-
An efficient and metal-free method has been developed for the direct synthesis of amides from readily available azobenzenes reacting with aroyl surrogates such as alcohols, methylarenes. A variety of amides were afforded in moderate to good yields through this reaction. It is another example reported by our group for the use of azobenzene as the new radical acceptor.
- Hong, Gang,Wu, Shengying,Zhu, Xiaoyan,Mao, Dan,Wang, Limin
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p. 436 - 441
(2015/12/31)
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- Amine Activation: Synthesis of N-(Hetero)arylamides from Isothioureas and Carboxylic Acids
-
A novel method for N-(hetero)arylamide synthesis based on rarely explored amine activation, rather than classical acid activation, is reported. The activated amines are easily prepared using a three-component reaction with commercial reagents. The new method shows a broad scope including challenging amides not (efficiently) accessible via classical protocols.
- Zhu, Yan-Ping,Sergeyev, Sergey,Franck, Philippe,Orru, Romano V. A.,Maes, Bert U. W.
-
supporting information
p. 4602 - 4605
(2016/09/28)
-
- Acidylation method of amine
-
The invention discloses an acidylation method of amine.The method includes the following steps that amine derivatives, hydrazide derivatives, organic peroxide and a catalyst are dissolved in a solvent and react at the temperature of 40-80 DEG C, and amide derivatives are obtained.The amide derivatives and hydrazide derivatives serve as initiators, the raw materials are easy to obtain and the number of varieties is large.Products obtained through the method are diverse in type, can be directly used and can also be used for other further reactions.The method is mild in reaction condition, simple in reaction operation and post-processing process, high in product yield and suitable for scale production.
- -
-
Paragraph 0043
(2016/10/10)
-
- 3D printing of a heterogeneous copper-based catalyst
-
One of the most important environmental challenges of modern society is to develop new catalysts that make possible chemical processes with reduced environmental impact. Catalyst immobilization is an appealing strategy that, in addition to facilitating catalyst recovery, has proved to give higher catalytic performance, since the solid support usually provides chemical, thermal, and mechanical stabilization to the catalytic species. In this work Cu/Al2O3 catalytic system with a woodpile porous structure is synthesized by 3D printing and then sintered at high temperature to generate a copper-supported rigid structure with high mechanical strength, a high surface-to-volume ratio, and controlled porosity. The catalytic species (Cu) are immobilized in the Al2O3 matrix to avoid the leaching of the metal into the reaction medium. Al2O3 was selected because it is a good material to obtain a structure with high mechanical stability after high-temperature treatment. The resulting device shows high catalytic efficacy and good recyclability and did not produce leaching of copper to the reaction medium in different Ullmann reactions. Ease of preparation, excellent reactivity, recyclability, and negligible metal contamination all make the 3D printing technique a good strategy for fabricating other types of metal/oxide heterogeneous catalytic systems.
- Tubío, Carmen R.,Azuaje, Jhonny,Escalante, Luz,Coelho, Alberto,Guitián, Francisco,Sotelo, Eddy,Gil, Alvaro
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p. 110 - 115
(2016/01/09)
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- Platinum nanowires catalyzed direct amidation with aldehydes and amines
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Different from the conventional synthesis methods and substrates, we designed a brand new method for synthesizing amides with platinum nanowires as catalysts and tert-butylhydroperoxide (TBHP) as the oxidant. Influence of factors, such as the catalyst, solvents, and the reaction temperature, were studied to determine the optimal reaction conditions. In addition, we explored the substrate generality and observed excellent yields.
- Xu, Dawei,Shi, Linyan,Ge, Danhua,Cao, Xueqin,Gu, Hongwei
-
p. 478 - 481
(2016/04/19)
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- A nanowire the platinum accepts method for catalytic synthesis of amides (by machine translation)
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The invention relates to a nanowire the platinum accepts method for catalytic synthesis of amides. Specifically, the method comprises the following steps: adding the reaction vessel in the nanowire the platinum accepts in alcoholic, decompression except mellow, further adding alchlor, reaction solvent, pyridine, amine compounds, aldehyde compound and an oxidizing agent, under the mixing conditions, the heating reaction in in oil bath, after purification by column chromatography, to obtain amides, wherein: the states the aldehyde class compounds, amine compounds, alchlor, pyridine, the platinum accepts molar ratio of the oxidizing agent and 0.5-3 : 0.5-3 : 0.1-0.5: 0.5-2 : 0.1% - 2% : 0.5-5, the heating of the reaction temperature is 80-140°C, the reaction time is 16-24 hours. Because the nanowire the platinum accepts as the catalyst, the invention is not only high catalytic activity, and the performance is stable, at the same time the method of the present invention can obtain a higher yield, mild condition, process is simple, easy to operate. (by machine translation)
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Paragraph 0041-0043
(2017/02/28)
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- Efficient synthesis of amides and esters from alcohols under aerobic ambient conditions catalyzed by a Au/mesoporous Al2O3 nanocatalyst
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An efficient heterogeneous Au/mesoporous alumina nanocatalyst has been successfully developed for the synthesis of amides and esters from simple building blocks of readily available alcohols and amines. The processes were simple and were performed at room temperature and atmospheric pressure of O2 to form the desired products with up to 97% isolated yield. The ability of Au/mesoporous alumina to catalyze these reactions under ambient conditions further enhances the sustainability of these chemical processes. Furthermore, the nanocatalyst was stable to air and water and could be recovered and reused easily. The enhanced catalytic activity of Au/mesoporous alumina might be attributed to the presence of negatively charged Au nanoparticles that could promote oxidation processes as well as the stability of the mesoporous alumina support calcined at a high temperature of 800°C. Gold for green: Gold nanoparticles supported on mesoporous alumina catalyze the efficient synthesis of amides and esters from simple building blocks of readily available alcohols and amines under ambient aerobic reaction conditions (R1=aryl, alkyl, and R2=H, alkyl).
- Chng, Leng Leng,Yang, Jinhua,Ying, Jackie Y.
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p. 1916 - 1925
(2015/06/16)
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- Formation of Amides from Imines via Cyanide-Mediated Metal-Free Aerobic Oxidation
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A new protocol for the direct formation of amides from imines derived from aromatic aldehydes via metal-free aerobic oxidation in the presence of cyanide is described. This protocol was applicable to various aldimines, and the desired amides were obtained in moderate to good yields. Mechanistic studies suggested that this aerobic oxidative amidation might proceed via the addition of cyanide to imines followed by proton transfer from carbon to nitrogen in the original imines, leading to carbanions of α-amino nitriles, which undergo subsequent oxidation with molecular oxygen in air to provide the desired amide compounds.
- Seo, Hong-Ahn,Cho, Yeon-Ho,Lee, Ye-Sol,Cheon, Cheol-Hong
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p. 11993 - 11998
(2016/01/09)
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- An efficient magnetic copper ferrite nanoparticle catalysed ligand and solvent free synthesis of N-aryl amide from aldoximes and iodobenzene
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A simple, efficient, and environmentally benign method has been reported for the synthesis of N-aryl amides using aldoximes and iodobenzene under ligand free and solvent free conditions and using magnetically separable copper ferrite nanoparticles as catalyst. The catalyst was characterised using XRD, FEG-SEM, EDAX, ICP-AES and TEM and tested for recyclability for up to five cycles.
- Sarode, Sachin A.,Bhojane, Jeevan M.,Nagarkar, Jayashree M.
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p. 105353 - 105358
(2015/12/30)
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- Copper-Catalyzed N-Benzoylation of Amines via Aerobic C-C Bond Cleavage
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A general copper/air catalytic system for selectively oxidative C-C bond cleavage of 1,2-diarylethan-1-one has been developed, giving aromatic aldehydes and N-benzoylation products of various amines in moderate to excellent yields. This research provides an alternative approach for the N-benzoylation of amine in mild and neutral conditions.
- Fan, Wenyou,Yang, Youqing,Lei, Jianhua,Jiang, Qijian,Zhou, Wang
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p. 8782 - 8789
(2015/09/15)
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- Synthesis of a copper(ii) complex covalently anchoring a (2-iminomethyl)phenol moiety supported on HAp-encapsulated-α-Fe2O3 as an inorganic-organic hybrid magnetic nanocatalyst for the synthesis of primary and secondary amides
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A novel hydroxyapatite-encapsulated-α-Fe2O3-based Cu(ii) organic-inorganic hybrid (interphase) catalyst was prepared. The prepared nanocatalyst provided an efficient, useful and green method for the oxidative amidation of aromatic aldehydes with ammonium hydrochloride and aniline hydrochloride, in short reaction times and good yields. The magnetic nature of the catalyst led to its easy recovery by an external magnetic field and convenient reuse.
- Mamaghani,Shirini,Sheykhan,Mohsenimehr
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p. 44524 - 44529
(2015/06/02)
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- Polyethylene glycol as a recyclable reaction medium for gold-catalysed direct oxidative amide synthesis from aldehydes and amines
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Polyethylene glycol (PEG) was used as the recyclable reaction medium for gold-catalysed oxidative amidation of aldehydes with amines by using tert-butyl hydroperoxide (TBHP, 70% aqueous) as the oxidant. The reaction proceeded efficiently to provide the corresponding products in moderate to good yields under mild conditions. Both the catalysts and solvent can be easily recovered and reused by simple extraction without significant loss of activity.
- Jiang, Hui-Liang,Zhao, Jie
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p. 654 - 656
(2016/01/25)
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- Effective nitration of anilides and acrylamides by tert-butyl nitrite
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Nitro compounds are important intermediates in synthetic organic chemistry and the chemical industry. Herein, the efficient copper-catalyzed [10% Cu(NO3)2·3H2O] nitration of anilides was developed by using TBN (tert-butyl nitrite) as a nitrating reagent to give the corresponding nitro-substituted aromatic products in good to excellent yields. The use of TBN also led to the selective nitration of acrylamides at room temperature to afford only the (E) isomer of the nitration product. A series of anilides and acrylamides with a broad array of functional groups were well-tolerated by this procedure. This synthetic method has many advantages, which include inexpensive starting materials, mild reaction conditions, a fast reaction rate, and high yields. A mechanistic investigation indicates that a nitro radical, which is generated from the thermal homolysis of TBN, is involved in the two nitration processes. The efficient nitration of both anilides and acrylamides was achieved by using TBN (tert-butyl nitrite) as a metal-free nitrating reagent. This synthetic method has many advantages such as mild reaction conditions, a fast reaction rate, good to excellent yields, and a broad substrate scope. Our investigation indicates that a nitro radical is involved in the reaction mechanism.
- Ji, Yi-Fei,Yan, Hong,Jiang, Qi-Bai
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p. 2051 - 2060
(2015/03/18)
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- Efficient cobalt-catalyzed C-N cross-coupling reaction between benzamide and aryl iodide in water
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A practical and efficient strategy for the N-arylation of benzamide catalysed by a Co(C2O4)·2H2O/dmeda system in water is reported. Under the optimized conditions, a wide variety of N-arylated products were obtained in good yields (up to 92%) using substituted aryl iodides.
- Tan, Bryan Yong-Hao,Teo, Yong-Chua
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supporting information
p. 7478 - 7481
(2014/12/11)
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- An efficient synthesis of amides from alcohols and azides catalyzed by a bifunctional catalyst Au/DNA under mild conditions
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A novel Au/DNA-catalyzed amidation from alcohols and azides was developed under mild conditions. Taking advantage of the water-soluble reversibility of this catalyst, the transformation could be carried out smoothly in water and the catalyst could be recovered and reused by a simple phase separation. This amidation reaction unitized the hydrogen transfer process and the oxidative coupling process synergistically in an atom economical and environmentally benign synthesis. the Partner Organisations 2014.
- Guo, Xuefeng,Tang, Lin,Yang, Yu,Zha, Zhenggen,Wang, Zhiyong
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supporting information
p. 2443 - 2447
(2014/05/06)
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- Copper catalyzed N-arylation between aryl halides and nitriles in water: An efficient tandem synthesis of benzanilides
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A series of benzanilide compounds were synthesized through copper-catalyzed tandem reactions. With the assistance of ionic liquid as phase transfer catalyst, aryl halides, and nitriles underwent a hydrolysis/coupling pathway to form benzanilides in water. Advantages of this reaction include the use of water as the environmental friendly solvent, short reaction time, and the tolerance of various functional groups. A proposed mechanism based on control experiments is also presented.
- Wang, Jichao,Yin, Xinchi,Wu, Jun,Wu, Datong,Pan, Yuanjiang
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p. 10463 - 10469
(2013/11/19)
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- 2-Aminopyrrolyl dilithium compounds: Synthesis, structural diversity, and catalytic activity for amidation of aldehydes with amines
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Five dilithium compounds containing bidentate dianionic pyrrolyl ligands, [{2-(CH3NCH2)C4H3N}Li 2(TMEDA)3] (1), {[μ-η5-2-[CH 3CH2NCH2]C4H3N]Li 2(TMEDA)}2 (2), {[μ-η5: η1-2-[(CH3)3CNCH2]C 4H3N]Li2(TMEDA)}2 (3), {[η5-2-[(CH3)2CHNCH2]C 4H3N]Li2 (TMEDA)}2 (4), and {[η5-2-[(CH2)5CHNCH2]C 4H3N]Li2(TMEDA)}2 (5), were synthesized, and their structural features were provided. Compounds 1-5 were proved to be a series of efficient catalysts for amidation reactions of aldehydes with amines in good to excellent yields under mild conditions.
- Guo, Zhiqiang,Liu, Qiao,Wei, Xuehong,Zhang, Yongbin,Tong, Hongbo,Chao, Jianbin,Guo, Jianping,Liu, Diansheng
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p. 4677 - 4683
(2013/09/23)
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- The synthesis of N-arylated amides via copper(II) triflate-catalyzed direct oxygenation and N-arylation of benzylamines with aryl iodides
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An efficient approach for the synthesis of N-arylated amides by copper(II) triflate-catalyzed direct oxygenation and N-arylation reaction of benzylamines with aryl iodides is reported. Various benzylamines and aryl iodides can participate in the reaction, providing a series of N-arylated amides in moderate to good yields.
- Xu, Mei,Zhang, Xiao-Hong,Shao, Yin-Lin,Han, Jiang-Sheng,Zhong, Ping
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supporting information
p. 2665 - 2670,6
(2012/12/12)
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- The synthesis of N-arylated amides via copper(II) triflate-catalyzed direct oxygenation and N-arylation of benzylamines with aryl iodides
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An efficient approach for the synthesis of N-arylated amides by copper(II) triflate-catalyzed direct oxygenation and N-arylation reaction of benzylamines with aryl iodides is reported. Various benzylamines and aryl iodides can participate in the reaction, providing a series of N-arylated amides in moderate to good yields.
- Xu, Mei,Zhang, Xiao-Hong,Shao, Yin-Lin,Han, Jiang-Sheng,Zhong, Ping
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supporting information
p. 2665 - 2670
(2013/01/15)
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