- NaI-mediated oxidative amidation of benzyl alcohols/aromatic aldehydes to benzamides via electrochemical reaction
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In this research, we have developed a mild electrochemical process for oxidative amidation of benzyl alcohols/aromatic aldehydes with cyclic amines into the corresponding benzamides. This electroorganic synthetic method proceeds using NaI as a redox mediator under ambient temperature in undivided cell, providing more than 25 examples of amide products in moderate to good yields. The benefits of this reaction include one-pot synthesis, open air condition, proceed in aqueous media and no requirement of external conducting salt, base and oxidant.
- Rerkrachaneekorn, Tanawat,Tankam, Theeranon,Sukwattanasinitt, Mongkol,Wacharasindhu, Sumrit
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supporting information
(2021/04/15)
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- Direct Amidation of Esters by Ball Milling**
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The direct mechanochemical amidation of esters by ball milling is described. The operationally simple procedure requires an ester, an amine, and substoichiometric KOtBu and was used to prepare a large and diverse library of 78 amide structures with modest to excellent efficiency. Heteroaromatic and heterocyclic components are specifically shown to be amenable to this mechanochemical protocol. This direct synthesis platform has been applied to the synthesis of active pharmaceutical ingredients (APIs) and agrochemicals as well as the gram-scale synthesis of an active pharmaceutical, all in the absence of a reaction solvent.
- Barreteau, Fabien,Battilocchio, Claudio,Browne, Duncan L.,Godineau, Edouard,Leitch, Jamie A.,Nicholson, William I.,Payne, Riley,Priestley, Ian
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supporting information
p. 21868 - 21874
(2021/09/02)
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- Solar and visible-light active nano Ni/g-C3N4photocatalyst for carbon monoxide (CO) and ligand-free carbonylation reactions
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In this study, we investigate the amino and alkoxycarbonylation reaction between various substituted aryl halides, benzyl iodides, and iodocyclohexane with different types of amines and alcohols in the absence of carbon monoxide gas and ligands. Similar reactions are carried out at high temperatures, in the presence of appropriate ligands, stoichiometric amounts of bases, and gaseous carbon monoxide, which endanger the health of organic chemists. We present a novel method that does not utilize ligands, bases, gaseous CO, and special conditions. This procedure is a redox reaction carried out by new economic nano Ni/g-C3N4at room temperature and under visible light. Mo(CO)6was used toin situgenerate CO, to resolve the problems caused by the use of CO gas. This protocol has the ability to be used on a gram scale by using a continuous flow reactor.
- Hosseini-Sarvari, Mona,Akrami, Zahra
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p. 956 - 969
(2021/02/26)
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- Method for preparing amide from carboxylic acid under irradiation of blue light by taking iridium and cobalt complexes as catalysts
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The invention relates to a method for preparing amide from carboxylic acid under the irradiation of blue light by taking iridium and cobalt complexes as catalysts, and belongs to the field of chemistry. The method comprises the following step of: by taking R substituted carboxylic acid and R1' and R2' substituted amines as raw materials, triphenylphosphine as a deoxidizing agent, [Ir(dF(CF3)ppy)2(dtbbpy)]PF6 as a photocatalyst and Co(dmgH)(dmgH2)Cl2 as a metal complex catalyst, reacting in dichloromethane in an inert atmosphere and under the irradiation of blue light to obtain an amide compound, wherein R is an aryl group, a heteroaryl group, a protected amino group, a substituted alkyl group, a substituted aryl group or a substituted protected amino group, R1' is a hydrogen group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and R2' is a hydrogen group, a substituted alkyl group, a phenyl group or a substituted phenyl group.
- -
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Paragraph 0041-0042
(2021/05/12)
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- Copper and N-Heterocyclic Carbene-Catalyzed Oxidative Amidation of Aldehydes with Amines
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A one-pot two-step oxidative process has been developed for the tert-butyl hydroperoxide mediated transformation of aldehydes and amines into amides catalyzed by copper(I) iodide and an N-heterocyclic carbene. The process is additive-free and does not require the amine to be transformed into its hydrochloride salts. The method is simple and practicable, has a broad substrate scope, and uses economical, feasible, and abundant reagents.
- Singh, Ashmita,Narula, Anudeep Kumar
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supporting information
p. 718 - 722
(2021/02/26)
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- Visible-Light-Mediated Oxidative Amidation of Aldehydes by Using Magnetic CdS Quantum Dots as a Photocatalyst
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A magnetic CdS quantum dot (Fe3O4/polydopamine (PDA)/CdS) was synthesized through a facile and convenient method from inexpensive starting materials. Characterization of the prepared catalyst was performed by means of FTIR spectrosco
- Xu, Ling,Zhang, Shuai-Zheng,Li, Wei,Zhang, Zhan-Hui
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p. 5483 - 5491
(2021/03/01)
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- Dilithium Amides as a Modular Bis-Anionic Ligand Platform for Iron-Catalyzed Cross-Coupling
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Dilithium amides have been developed as a bespoke and general ligand for iron-catalyzed Kumada-Tamao-Corriu cross-coupling reactions, their design taking inspiration from previous mechanistic and structural studies. They allow for the cross-coupling of alkyl Grignard reagents with sp2-hybridized electrophiles as well as aryl Grignard reagents with sp3-hybridized electrophiles. This represents a rare example of a single iron-catalyzed system effective across diverse coupling reactions without significant modification of the catalytic protocol, as well as remaining operationally simple.
- Neate, Peter G.N.,Zhang, Bufan,Conforti, Jessica,Brennessel, William W.,Neidig, Michael L.
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supporting information
p. 5958 - 5963
(2021/08/18)
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- Visible-Light Photoredox-Catalyzed Amidation of Benzylic Alcohols
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A new photocatalyzed route to amides from alcohols and amines mediated by visible light is presented. The reaction is carried out in ethyl acetate as a solvent. Ethyl acetate can be defined a green and bio-based solvent. The starting materials such as the energy source are easily available, stable, and inexpensive. The reaction has shown to be general and high yielding.
- Gaspa, Silvia,Farina, Andrea,Tilocca, Mariella,Porcheddu, Andrea,Pisano, Luisa,Carraro, Massimo,Azzena, Ugo,De Luca, Lidia
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p. 11679 - 11687
(2020/10/23)
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- Double carbonylation of iodoarenes in the presence of a pyridinium SILP-Pd catalyst
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The efficiency of a palladium catalyst, immobilised on a supported ionic liquid phase (SILP) with adsorbed 1-butyl-4-methylpyridinium chloride, was investigated in aminocarbonylation reactions. Double carbonylation was found to be the main reaction using different iodoarenes and aliphatic amines as substrates. Application of aniline derivatives as nucleophiles led to the exclusive formation of substituted benzamides. The stabilisation effect of the adsorbed pyridinium ionic liquid was compared to that of imidazolium and phosphonium derivatives. It was proved that the pyridinium SILP-palladium catalyst could be reused in at least 10 cycles. Recyclability was tested in five successive runs for all of the substrates.
- Nagy, Enik?,Nagy, Petra,Papp, Máté,Skoda-F?ldes, Rita,Urbán, Béla
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- Two-step continuous flow synthesis of amide via oxidative amidation of methylarene
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A green and efficient method for the synthesis of amides has been developed through oxidative amidation between methylarenes with amines in a two-step continuous flow system. This method integrates methylarene oxidation and amide formation into a single operation which is usually accomplished separately. Oxidation with tert-butyl hydroperoxide (TBHP) as “green” oxidant, the synthesis of amides under mild reaction conditions in continuous flow system and the utilization of methylarenes as starting material make this methodology novel and environment friendly. The practical value of this method is highlighted through the synthesis of high-profile pharmaceutical agents, acetylprocainamide.
- Fang, Zheng,Guo, Kai,He, Wei,Liu, Chengkou,Shi, Tingting,Yang, Yuhang,Yang, Zhao,Zhang, Zhimin
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supporting information
(2020/02/28)
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- Tandem Photoredox Catalysis: Enabling Carbonylative Amidation of Aryl and Alkylhalides
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We report a new visible-light-mediated carbonylative amidation of aryl, heteroaryl, and alkyl halides. A tandem catalytic cycle of [Ir(ppy)2(dtb-bpy)]+ generates a potent iridium photoreductant through a second catalytic cycle in the presence of DIPEA, which productively engages aryl bromides, iodides, and even chlorides as well as primary, secondary, and tertiary alkyl iodides. The versatile in situ generated catalyst is compatible with aliphatic and aromatic amines, shows high functional-group tolerance, and enables the late-stage amidation of complex natural products.
- Connell, Timothy U.,Forni, José A.,Micic, Nenad,Polyzos, Anastasios,Weragoda, Geethika
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supporting information
p. 18646 - 18654
(2020/08/21)
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- Amidation of Aldehydes with Amines under Mild Conditions Using Metal-Organic Framework Derived NiO@Ni Mott-Schottky Catalyst
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Here we report a facile method for the synthesis of nickel oxide-nickel (NiO@Ni) Mott-Schottky catalyst employing metal-organic framework (MOF) as the precursor. A direct amidation protocol of aldehydes with amines has been optimized under mild conditions using NiO@Ni Mott-Schottky catalyst and it shows far better catalytic activity than the NiO?Ni nanoparticles prepared from simple Ni2+ salt under similar reaction conditions. The heterogeneous catalyst is robust, recyclable and efficient to provide comparable yield to costly ligand-based homogeneous Ni catalysts. The scope of the reaction protocol has been explored with variably substituted substrates. The reaction initiates by homolytic cleavage of peroxide and proceeds through radical mechanism.
- Goel, Bharat,Vyas, Ved,Tripathi, Nancy,Kumar Singh, Ajit,Menezes, Prashanth W.,Indra, Arindam,Jain, Shreyans K.
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p. 5743 - 5749
(2020/09/09)
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- Metal-Free C-N or C-C Bond Cleavages of α-Azido Ketones: An Oxidative-Amidation Strategy for the Synthesis of α-Ketothioamides and Amides
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A novel metal-free oxidative-amidation strategy for the synthesis of α-ketothioamides and amides from α-azido ketones was developed. The C-H bond thionation of α-azido ketones with elemental sulfur could form α-ketothioacyl azide, which was then nucleophilically attacked by amines, causing the cleavage of the C-N bond to afford α-ketothioamides, while amides could be formed with the release of nitrogen gas and cyano anion in the presence of PhI(OAc)2 by selective C-C bond cleavage.
- Yu, Pei,Wang, Yuwei,Zeng, Zhigang,Chen, Yunfeng
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p. 14883 - 14891
(2019/11/11)
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- Gram-Scale, Cheap, and Eco-Friendly Iron-Catalyzed Cross-Coupling between Alkyl Grignard Reagents and Alkenyl or Aryl Halides
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A new robust methodology for gram-scale iron-catalyzed cross-coupling between alkyl Grignard reagents and alkenyl or aryl halides is developed. This method does not require toxic additives such as NMP or expensive ligands. Its efficiency relies on the use of simple alkoxide magnesium salts as additives. On the basis of these results, a new procedure for one-pot synthesis of substituted benzamides from chloroesters is also proposed.
- Cahiez, Gérard,Lefèvre, Guillaume,Moyeux, Alban,Guerret, Olivier,Gayon, Eric,Guillonneau, Lo?c,Lefèvre, Nicolas,Gu, Qinzhuo,Zhou, Edouard
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supporting information
p. 2679 - 2683
(2019/04/30)
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- Supported Palladium Nanoparticles that Catalyze Aminocarbonylation of Aryl Halides with Amines using Oxalic Acid as a Sustainable CO Source
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Polystyrene-supported palladium (Pd@PS) nanoparticles (NPs) have been used to catalyze the aminocarbonylation of aryl halides with amines using oxalic acid as a CO source for the first-time for the synthesis of amides. Furthermore, o-iodoacetophenones participated in amidation and cyclization reactions to give isoindolinones in a single step following a concerted approach. Oxalic acid has been used as a safe, environmentally benign and operationally simple ex situ sustainable CO source under double-layer-vial (DLV) system for different aminocarbonylation reactions. Catalyst stability under a CO environment is a challenging task, however, Pd@PS was found to be recyclable and applicable for a vast substrate scope avoiding regeneration steps. Easy handling of oxalic acid, additive and base-free CO generation, catalyst stability and effortless catalyst separation from the reaction mixture by filtration and introduce of DLV are the added advantages to make the overall process a sustainable approach.
- Bal Reddy,Ram, Shankar,Kumar, Ajay,Bharti, Richa,Das, Pralay
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supporting information
p. 4067 - 4071
(2019/02/27)
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- Visible light-induced transformation of aldehydes to esters, carboxylic anhydrides and amides
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A transition metal- and organophotocatalyst free synthesis of esters, carboxylic anhydrides and amides from aldehydes induced by visible-light has been reported. The proposed methodology can be carried out by the use of sunlight or artificial visible light as a blue LED source. The methodology has a very broad applicability and the desired products are obtained in very satisfactory yields.
- Gaspa, Silvia,Raposo, Inês,Pereira, Leonor,Mulas, Gabriele,Ricci, Pier Carlo,Porcheddu, Andrea,De Luca, Lidia
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p. 10711 - 10715
(2019/07/15)
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- Carbon bridged bis-amide-based rare-earth amine compound and its preparation and with [...][...] synthesis reaction in the application of the
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The invention discloses a carbon-bridged diacylamino rare earth amide with a general formula of {LLn[N(SiMe3)2]}2, wherein Ln is a rare earth metal selected from lanthanum, neodymium, samarium and yttrium, L represents a carbon-bridged diacylamino ligand, and n may be 1, 2 or 3 and can represent different ligands. The chemical structural formula of the carbon-bridged diacylamino rare earth amide differs with changes of the rare earth metal and the ligand. The invention targetedly discloses four chemical structural formulas of the rare earth amide as shown in the general formula. The carbon-bridged diacylamino rare earth amide provided by the invention is simple to synthesize, has definite structure and high yield and is easy to separate and purify. The invention also provides a preparation method for the rare earth amide and a method for applying the rare earth amide as a catalyst for catalysis of amidation of aldehyde and amine. The application method has the advantages of mild conditions, high activity, good selectivity, a wide substrate adaptation scope, a small catalyst amount and high product yield.
- -
-
Paragraph 0102; 0103
(2019/04/02)
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- Convenient metal-free direct oxidative amidation of aldehyde using dibromoisocyanuric acid under mild conditions
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A facile method for the direct synthesis of amides from aldehydes is described. Amide bonds were synthesized by an oxidative amidation in the presence of dibromoisocyanuric acid (DBI). Treatment of aromatic and aliphatic aldehydes with dibromoisocyanuric acid generated acyl bromide intermediates, which were employed to react with a variety of secondary and primary amines to give amides. Through this reaction method, various amides were synthesized directly from aldehydes under mild conditions in high yields and short times. This facile and efficient procedure provides potential strategy for the direct synthesis of amides from aldehydes.
- Kang, Soosung,La, Minh Thanh,Kim, Hee-Kwon
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supporting information
p. 3541 - 3546
(2018/08/29)
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- Ruthenium(II)-NNN-Pincer-Complex-Catalyzed Reactions Between Various Alcohols and Amines for Sustainable C?N and C?C Bond Formation
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An air and moisture stable 2-hydroxypyridine based bifunctional ruthenium NNN-pincer complex catalyzed efficient (TON=42840) N-alkylation of amines under mild conditions. Surprisingly, with cyclic secondary amines this methodology selectively produced only amides. Notably, N-methylation of several amines was achieved by using methanol as a green methylating agent. Furthermore, with lower catalyst loading (0.2 mol%) and shorter reaction time (6 h) numerous substituted quinolines were synthesized from 2-aminobenzyl alcohols and secondary alcohols. The effectiveness of this protocol was further extended by successfully synthesizing 2-alkylaminoquinolines in a one-pot fashion from amino alcohol, aliphatic nitriles, and alcohols. Gram scale synthesis of various compounds was also investigated to demonstrate the synthetic applicability of this methodology. (Figure presented.).
- Maji, Milan,Chakrabarti, Kaushik,Paul, Bhaskar,Roy, Bivas Chandra,Kundu, Sabuj
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supporting information
p. 722 - 729
(2018/01/01)
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- Organic ligand-free carbonylation reactions with unsupported bulk Pd as catalyst
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Herein, surprising results for bulk Pd-catalyzed carbonylation reactions are presented. Three types of carbonylation reactions can be realized efficiently under organic ligand-free conditions, namely, hydroaminocarbonylation of olefins, aminocarbonylation of aryl iodides and oxidative carbonylation of amines, which almost cover all the known mechanisms in carbonylation reactions. Notably, the bulk Pd catalyst system exhibited better catalytic activity than the classical homogeneous PdCl2/(2-OMePh)3P catalyst system. This study will create a momentous and new field of green carbonylation reactions.
- Liu, Shujuan,Wang, Hongli,Dai, Xingchao,Shi, Feng
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supporting information
p. 3457 - 3462
(2018/08/06)
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- An efficient procedure for chemoselective amidation from carboxylic acid and amine (ammonium salt) under mild conditions
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Presented here is an efficient one-pot and catalyst-free procedure for the synthesis of amides starting from carboxylic acids and amine/ammonium salts using 2,2-dichloro-1,3-diisopropylimidazolidine-4,5-dione as the coupling agent. Reactions can proceed smoothly even with those bearing thermosensitive group(s) at ambient temperature, and the corresponding products of primary, secondary and tertiary amides can be afforded in moderate to excellent yields of up to 96%.
- Li, Jianhui,He, Shaopo,Fu, Haiqing,Chen, Xin,Tang, Min,Zhang, Dela,Wang, Bo
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p. 2289 - 2303
(2017/12/26)
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- I2-Catalyzed Oxidative Amidation of Benzylamines and Benzyl Cyanides under Mild Conditions
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We report a novel and efficient method for the oxidation of benzylic carbons (amines and cyanides) into corresponding benzamides using a catalytic amount of I2 and TBHP as the green oxidant via the C-H bond cleavage of the benzylic carbon under mild reaction conditions. According to the literature survey, this is the first report for the oxidative amidation of benzylamines and decyanation of benzyl cyanides in one pot under metal-free conditions.
- Nageswara Rao, Sadu,Reddy, N. Naresh Kumar,Samanta, Supravat,Adimurthy, Subbarayappa
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p. 13632 - 13642
(2017/12/26)
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- Copper-catalyzed one-pot oxidative amidation between methylarenes and amines
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A new method for the direct one-pot oxidative amidation between methylarenes and amines catalyzed by copper has been developed. This method integrates methylarene oxidation and amide bond formation, which are usually accomplished separately, into a single operation. In addition, the reaction provides a relatively high yield and has a wide substrate scope. Moreover, the starting reagents are abundant and available in a convenient way at a cheaper price.
- Yang, Yuhang,Gu, Jiajia,Fang, Zheng,Yang, Zhao,Wei, Ping,Guo, Kai
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p. 22797 - 22801
(2017/07/10)
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- Palladium-Catalyzed Oxidative Carbonylation of Aryl Hydrazines with CO and O2 at Atmospheric Pressure
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Palladium-catalyzed aerobic oxidative aminocarbonylation and alkoxycarbonylation reactions with aryl hydrazines as coupling partners have been developed. The oxidative carbonylation of aryl hydrazines proceeded smoothly at atmospheric pressure CO, employi
- Tu, Yongliang,Yuan, Lin,Wang, Tao,Wang, Changliu,Ke, Jiamei,Zhao, Junfeng
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p. 4970 - 4976
(2017/05/12)
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- Ortho lithiation-in situ borylation of substituted morpholine benzamides
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Morpholine amides are cheap and safe alternative to Weinreb amides as acylating agents of organometallic species. Herein, the in-situ lithiation/borylation of 18 ortho- meta- and para-substituted morpholine benzamides has been investigated. 10 of the 18 substrates provided the desired boronic esters as the major isomer (>90% regioselectivity) in crude isolated yields ranging from 68 to 93%. The synthetic usability of such building blocks was subsequently illustrated via the synthesis of a kinase inhibitor.
- Cederbalk, Anna,Lysén, Morten,Kehler, Jan,Kristensen, Jesper L.
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p. 1576 - 1582
(2017/03/08)
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- Mono- and double carbonylation of aryl iodides with amine nucleophiles in the presence of recyclable palladium catalysts immobilised on a supported dicationic ionic liquid phase
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Silica modified with organic dicationic moieties proved to be an excellent support for palladium catalysts used in the aminocarbonylation of aryl iodides. By an appropriate choice of the reaction conditions, the same catalyst could be used for selective mono- or double carbonylations leading to amide and α-ketoamide products, respectively. The best catalyst could be recycled for at least 10 consecutive runs with a loss of palladium below the detection limit. By the application of the new support, efficient catalyst recycling could be achieved under mild reaction conditions (under low pressure and in a short reaction time). Palladium-leaching data support a mechanism with dissolution - re-precipitation of the active palladium species.
- Papp,Szabó,Srankó,Sáfrán,Kollár,Skoda-F?ldes
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p. 44587 - 44597
(2017/09/26)
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- Copper-Catalyzed Aerobic Oxidative Amidation of Benzyl Alcohols
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A Cu-catalyzed synthesis of amides from alcohols and secondary amines using the oxygen in air as the terminal oxidant has been developed. The methodology is operationally simple requiring no high pressure equipment or handling of pure oxygen. The commercially available, nonprecious metal catalyst, Cu(phen)Cl2, in conjunction with di-tert-butyl hydrazine dicarboxylate and an inorganic base provides a variety of benzamides in moderate to excellent yields. The pKa of amine conjugate acid and electronics of alcohol were shown to impact the selection of base for optimal reactivity. A mechanism consistent with the observed reactivity trends, KIE, and Hammett study is proposed.
- Krabbe, Scott W.,Chan, Vincent S.,Franczyk, Thaddeus S.,Shekhar, Shashank,Napolitano, José G.,Presto, Carmina A.,Simanis, Justin A.
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p. 10688 - 10697
(2016/11/29)
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- Copper-catalyzed one-pot oxidative amidation of alcohol to amide via C-H activation
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A one-pot oxidative amidation of both aliphatic and aromatic alcohols with N-chloramines, prepared in situ from many types of primary and secondary amines, was developed. This cross-coupling reaction integrates alcohol oxidation and amide bond formation, which are usually accomplished separately, into a single operation. And it was green, simple and convenient, which has a wide substrate scope and makes use of cheap, abundant, and easily available reagents. The practical value of this method is highlighted through the synthesis of a high-profile pharmaceutical agent, acetylprocainamide.
- Gu, Jiajia,Fang, Zheng,Yang, Yuhang,Yang, Zhao,Wan, Li,Li, Xin,Wei, Ping,Guo, Kai
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p. 89413 - 89416
(2016/10/03)
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- Copper-catalyzed and iodide-promoted aerobic C-C bond cleavage/C-N bond formation toward the synthesis of amides
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A copper-catalyzed and iodide-promoted aerobic C-C bond cleavage/C-N bond formation reaction between ketone and simple amine was developed toward the synthesis of amides, which are useful synthetic intermediates in organic synthesis and important skeletons of biologically active molecules. Notably, the reaction conditions are very mild, and preliminary mechanistic investigations indicate that molecular oxygen might be involved in the C-C bond cleavage process.
- Wu, Kun,Huang, Zhiliang,Ma, Yiyang,Lei, Aiwen
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p. 24349 - 24352
(2016/03/15)
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- Covalent triazine framework-supported palladium as a ligand-free catalyst for the selective double carbonylation of aryl iodides under ambient pressure of CO
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Carbonylation of aryl iodides with amines under atmospheric pressure of CO, catalyzed by Pd/CTFs (covalent triazine frameworks) without any specific additives, leads to the highly selective synthesis of α-ketoamides.
- Wang, Zhifang,Liu, Cuibo,Huang, Yi,Hu, Yuchen,Zhang, Bin
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supporting information
p. 2960 - 2963
(2016/02/19)
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- Direct oxidative amination of aromatic aldehydes with amines in a continuous flow system using a metal-free catalyst
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A novel method for metal-free oxidative amination of aromatic aldehydes and alcohols in the presence of H2O2/NaBr/H+ within 25 min in a continuous flow system has been developed. A series of different substrates were tested and the corresponding products were obtained in good yields .
- Gu, Jiajia,Fang, Zheng,Liu, Chengkou,Li, Xin,Wei, Ping,Guo, Kai
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p. 72121 - 72126
(2016/08/09)
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- Synthesis and characterization of bridged bis(amidato) rare earth metal amides and their applications in C-N bond formation reactions
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Based on three bisamide proligands H2Ln (n = 1-3) (H2L1 = [(Me3C6H2CONHCH2)2CH2], H2L2 = [(Me3C6H2CONHCH2)2C(CH3)2], H2L3 = [Me3C6H2CONH(CH2)2]2NCH3), eight bis(amidato) trivalent rare-earth metal amides {LnRE[N(TMS)2]}2 (n = 1, RE = La (1), Sm (2), Nd (3), Y (4); n = 2, RE = La (5), Nd (6); n = 3, RE = La (7), Nd (8); TMS = SiMe3) were successfully synthesized by treatment of H2Ln with RE[N(TMS)2]3 in a 1:1 molar ratio. Complexes 3, and 5-8 were characterized by single-crystal X-ray diffraction, and NMR characterization was carried out for the La complexes 1, 5, 7 and the Y complex 4. These complexes exhibited high catalytic activities in both the direct amidation of aldehydes and the addition of amines with carbodiimine. It was found that the bis(amidato) rare earth metal amides bearing different linkers have different effects on the transformations and lanthanum and neodymium complexes performed better than others.
- Zhao, Bei,Xiao, Yang,Yuan, Dan,Lu, Chengrong,Yao, Yingming
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p. 3880 - 3887
(2016/03/05)
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- Palladium nanoparticles immobilized on an amine-functionalized MIL-101(Cr) as a highly active catalyst for oxidative amination of aldehydes
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The present work reports the synthesis of well dispersed palladium nanoparticles immobilized on an amino functionalized nanoscale metal-organic framework MIL-101(Cr), by using a facile polyol method. The resulting Pd/NH2-MIL-101(Cr) nanocomposite is established to be an active heterogeneous catalyst for oxidative amination of aldehydes under solvent free conditions using hydrogen peroxide as an oxidant. The synthesized Pd/NH2-MIL-101(Cr) is characterized by powder X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, field emission scanning electron microscopy, Brunauer-Emmett-Teller (BET) surface area analysis, Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and atomic absorption spectroscopy (AAS). The catalyst could easily be recovered and recycled without any significant loss of its catalytic activity.
- Saikia, Mrinal,Saikia, Lakshi
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p. 14937 - 14947
(2016/02/19)
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- CuCl/TBHP catalyzed synthesis of amides from aldehydes and amines in water
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A CuCl/TBHP catalyzed amidation of aldehydes with amine under aqueous media is described. Both aliphatic and aromatic aldehydes coupled with a variety of amines under the reaction conditions employed.
- Lu, Shao-Yi,Badsara, Satpal Singh,Wu, Yi-Chun,Reddy, Daggula Mallikarjuna,Lee, Chin-Fa
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supporting information
p. 633 - 636
(2016/01/26)
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- A two-step continuous flow synthesis of amides from alcohol using a metal-free catalyst
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Metal-free oxidative amination of aromatic alcohols in the presence of TBHP provides convenient access to amides in 86-96% yield under mild reaction conditions within 15 min in a two-step continuous flow reactor system. This method avoids expensive transition metal catalysts and integrates alcohol oxidation and amide bond formation, which are usually accomplished separately, into a single operation.
- Gu, Jiajia,Fang, Zheng,Liu, Chengkou,Yang, Zhao,Li, Xin,Wei, Ping,Guo, Kai
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p. 95014 - 95019
(2015/11/24)
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- Iodine-catalyzed efficient amide formation from aldehydes and amines
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An efficient iodine-catalyzed radical oxidative amidation of aldehydes with amines has been developed. This methodology was employed to prepare amides in good to excellent yields with the advantages of wide functional group tolerance and operational simplicity.
- Wang, Peng,Xia, Jiaxuan,Gu, Yueqing
-
supporting information
p. 7120 - 7123
(2015/12/01)
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- Chloroform as a Carbon Monoxide Precursor: In or Ex Situ Generation of CO for Pd-Catalyzed Aminocarbonylations
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Conditions for the rapid hydrolysis of chloroform to carbon monoxide (CO) using heterogeneous CsOH·H2O are described. CO and 13CO can be generated cleanly and rapidly under mild conditions and can be captured either in or ex situ in palladium-catalyzed aminocarbonylation reactions. Utilizing only 1-3 equiv of CO allows for the aminocarbonylation of aryl, vinyl, and benzyl halides with a wide variety of primary and secondary amines giving amide products in good to excellent yields. (Chemical Equation Presented).
- Gockel, Samuel N.,Hull, Kami L.
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supporting information
p. 3236 - 3239
(2015/07/15)
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- Direct oxidative amidation between methylarenes and amines in water
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An environmentally friendly direct oxidative amidation between methylarenes and free amines was developed. The aromatic amide could be prepared efficiently from raw chemicals by employing TBHP as a "green" oxidant with co-catalysis of TBAI and FeCl3 in water.
- Wang, Tao,Yuan, Lin,Zhao, Zhenguang,Shao, Ailong,Gao, Meng,Huang, Yangfei,Xiong, Fei,Zhang, Huali,Zhao, Junfeng
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supporting information
p. 2741 - 2744
(2015/05/27)
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- Double carbonylation of aryl iodides with amines under an atmospheric pressure of carbon monoxide using sulfur-modified Au-supported palladium
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A double carbonylation of aryl iodides with amines proceeded smoothly under an atmospheric pressure of carbon monoxide by using palladium nanoparticles (Pd NPs) leached from a sulfur-modified Au-supported palladium material (SAPd), producing α-ketoamides in good to excellent yields. This journal is
- Saito, Nozomi,Taniguchi, Takahisa,Hoshiya, Naoyuki,Shuto, Satoshi,Arisawa, Mitsuhiro,Sato, Yoshihiro
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supporting information
p. 2358 - 2361
(2015/04/22)
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- Photoinduced Aminocarbonylation of Aryl Iodides
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Transition metal-catalyzed aminocarbonylation of aryl halides with CO and amines, pioneered by Heck and co-workers in the 1970s, is among the most commonly employed reactions to make aromatic amides. A catalyst-free aminocarbonylation of aryl iodides with CO and amines, which simply uses photoirradiation conditions by Xe-lamp, has now been developed. This methodology shows broad functional-group tolerance, including that of heteroaromatic amides. A hybrid radical/ionic chain mechanism, involving electron transfer from zwitterionic radical intermediates generated by nucleophilic attack of amines to aroyl radicals, is proposed.
- Kawamoto, Takuji,Sato, Aoi,Ryu, Ilhyong
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supporting information
p. 14764 - 14767
(2015/10/19)
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- Anionic phenoxy-amido rare-earth complexes as efficient catalysts for amidation of aldehydes with amines
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A series of anionic organo-rare-earth amido complexes stabilized by dianionic phenoxy-amido ligands were prepared and their catalytic behavior for amidation reactions of aldehydes with amines was elucidated. Amine elimination reaction of Ln[N(SiMe3)2]3(μ-Cl)Li(THF)3 with an equimolar of lithium aminophenoxy {[HNO]1Li(THF)}2, which was prepared by the reaction of [HNOH]1 {[HNOH]1 = N-p-fluoro-phenyl(2-hydroxy-3,5-di-tert-butyl)benzylamine} with one equivalent of n-BuLi in tetrahydrofuran (THF) in situ, gave the anionic phenoxy-amido rare earth amido complexes [NO]12Ln[N(SiMe3)2][Li(THF)]2 [Ln = Y (1), Yb (2), Sm (3), Nd (4)] in high isolated yields. Similar reactions of Ln[N(SiMe3)2]3(μ-Cl)Li(THF)3 with {[HNO]2Li(THF)}2, and {[HNO]3Li(THF)}2 in THF gave the anionic rare-earth amides [NO]22Ln[N(SiMe3)2][Li(THF)]2 [Ln = Sm (5), Nd (6)] and [NO]32Ln[N(SiMe3)2][Li(THF)]2 [Ln = Sm (7), Nd (8)] {[HNOH]2 = N-p-chloro-phenyl(2-hydroxy-3,5-di-tert-butyl)benzylamine; [HNOH]3 = N-p-bromo-phenyl(2-hydroxy-3,5-di-tert-butyl)benzylamine}, respectively. All of these complexes were fully characterized. X-ray structural determination revealed that these complexes are isostructural, and have solvated monomeric structures. Each of the rare-earth ions is coordinated by two phenoxy-amido ligands and one N(SiMe3)2 group, and the coordination geometry can be described as a distorted trigonal bipyramid. Each of the lithium atoms is surrounded by one aryloxo group, one amido group and one THF molecule, and the coordination geometry can be described as a trigonal plane. The catalytic behavior of these rare-earth amides for the amidation reaction of aldehyde with amine was elucidated. It was found that these complexes are efficient catalysts for this transformation to produce amides in good to excellent yields under mild reaction conditions, and in some cases, diacylamide compounds can be prepared conveniently.
- Wang, Chao,Huang, Lingling,Lu, Min,Zhao, Bei,Wang, Yaorong,Zhang, Yong,Shen, Qi,Yao, Yingming
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p. 94768 - 94775
(2015/11/24)
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- Co2(CO)8 as a convenient in situ CO source for the direct synthesis of benzamides from aryl halides (Br/I) via aminocarbonylation
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A fast, mild, and functional group tolerant method for the direct synthesis of benzamides from aryl halides (Br, I) via aminocarbonylation, using solid Co2(CO)8 as a convenient CO source, has been demonstrated. The developed method is applicable to a wide variety of 1 and cyclic and acyclic 2 amines. Nitro substituted (o, m and p) aryl halides have easily been converted to the corresponding benzamides, without the reduction of the nitro group, in high yields using this in situ carbonylation methodology under microwave irradiation.
- Baburajan, Poongavanam,Elango, Kuppanagounder P.
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supporting information
p. 1006 - 1010
(2014/02/14)
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- Co2(CO)8 as a convenient in situ CO source for the direct synthesis of benzamides from aryl halides (Br/I) via aminocarbonylation
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A fast, mild, and functional group tolerant method for the direct synthesis of benzamides from aryl halides (Br, I) via aminocarbonylation, using solid Co2(CO)8 as a convenient CO source, has been demonstrated. The developed method is applicable to a wide variety of 1° and cyclic and acyclic 2°amines. Nitro substituted (o, m and p) aryl halides have easily been converted to the corresponding benzamides, without the reduction of the nitro group, in high yields using this in situ carbonylation methodology under microwave irradiation.
- Baburajan, Poongavanam,Elango, Kuppanagounder P.
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supporting information
p. 1006 - 1010
(2015/02/19)
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- Chitosan: An efficient recyclable catalyst for transamidation of carboxamides with amines under neat conditions
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A novel chitosan-catalyzed transamidation of carboxamides with amines under solvent-free conditions is described. A series of amide derivatives as well as more challenging aryl and alkyl amines with long-chain alkyl substituents could be selectively converted into the corresponding transamidation products, which are frequently found in biologically active compounds and pharmaceuticals. Under similar reaction conditions benzo[d]heterocycles were also obtained via a one-pot synthesis through transamidation and subsequent dehydration. Recyclability of chitosan was demonstrated, with quantitative yields of products obtained without any loss of catalytic activity. the Partner Organisations 2014.
- Nageswara Rao, Sadu,Chandra Mohan, Darapaneni,Adimurthy, Subbarayappa
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supporting information
p. 4122 - 4126
(2014/10/15)
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- Mild and direct conversion of esters to morpholine amides using diisobutyl(morpholino)aluminum: Application to efficient one-pot synthesis of ketones and aldehydes from esters
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Morpholine amide intermediates, which are easily prepared by aminolysis of various esters with diisobutyl(morpholino)aluminum, react with organolithium and reducing agents (DIBALH or LDBMA) without isolation of the aminolysis intermediates to give ketones in 83-95% yields and aldehydes quantitatively.
- Jeon, Ah Ram,Kim, Min Eai,Park, Jae Kyo,Shin, Won Kyu,An, Duk Keun
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p. 4420 - 4424
(2014/06/10)
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- Visible light induced photocatalytic conversion of enamines into amides
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A series of enamines were photocatalytically cleaved to produce amide products under simple visible-light irradiation from a 45 W household light bulb. Mechanistically, the reactions appear to involve photosensitized formation of a singlet oxygen intermediate and a subsequent [2+2] cycloaddition event. Georg Thieme Verlag Stuttgart, New York.
- Li, Jing,Cai, Shunyou,Chen, Jietao,Zhao, Yaohong,Wang, David Zhigang
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p. 1626 - 1628
(2014/07/08)
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- Mesoporous poly-melamine-formaldehyde stabilized palladium nanoparticle (Pd@mPMF) catalyzed mono and double carbonylation of aryl halides with amines
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A new mesoporous poly-melamine-formaldehyde material supported Pd nano catalyst (mPMF-Pd0) has been synthesized and characterized by thermogravimetric analysis (TGA), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS), high-resolution transmission electron microscopy (HRTEM), UV-vis diffuse reflection spectroscopy (DRS), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and a N2 adsorption study. The mPMF-Pd0 material showed very good catalytic activity in the field of mono and double amino carbonylation of aryl bromides/iodides. Moreover, the catalyst is easily recoverable and can be reused six times without appreciable loss of catalytic activity in the above reactions. So, the highly dispersed and strongly bound palladium(0) sites in the mPMF-Pd0 could be responsible for the observed high activities. Due to strong binding with the functional groups of the polymer, no evidence of leached Pd from the catalyst during the course of reaction occurred, suggesting true heterogeneity in the catalytic process. This journal is
- Molla, Rostam Ali,Iqubal, Md. Asif,Ghosh, Kajari,Roy, Anupam Singha,Kamaluddin,Islam, Sk. Manirul
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p. 48177 - 48190
(2014/12/10)
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- Silica nanosphere-supported palladium(II) furfural complex as a highly efficient and recyclable catalyst for oxidative amination of aldehydes
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The present work reports the fabrication of a novel and highly efficient silica nanospheres-based palladium catalyst (SiO2@APTES@Pd-FFR) via immobilization of a palladium complex onto silica nanospheres functionalized with 3-aminopropyltriethoxysilane (APTES), and its catalytic application for the oxidative amination of aldehydes to yield commercially important amides. The structure of the nano-catalyst was confirmed by Solid-state 13C CPMAS and 29Si CPMAS NMR spectroscopy, Brunauer-Emmett-Teller (BET) surface area analysis, Fourier transform infrared spectroscopy (FT-IR), Energy dispersive X-ray fluorescence spectroscopy (ED-XRF), Atomic absorption spectroscopy (AAS), Transmission electron microscopy (TEM) and elemental analysis. The nano-catalyst was found to be highly effective for the oxidative amination of aldehydes using hydrogen peroxide as an environmentally benign oxidant to give amides. The effect of various reaction parameters such as temperature, amount of catalyst, reaction time, type of solvent, oxidant used, substrate to oxidant ratio etc. have been demonstrated to achieve high catalytic efficacy. Moreover, this nanostructured catalyst could be recovered with simplicity and reused for several cycles without any significant loss in its catalytic activity. In addition, the stability of the reused nano-catalyst was proved by FT-IR and HRTEM techniques. It is worth noting that the features of mild reaction conditions, simple work-up procedure, high product yield, no use of toxic organic solvents, high turn-over frequency (TOF), and easy recovery and reusability of the present quasi-homogeneous nano-catalyst make this protocol an attractive alternative to the existing catalytic methods for the oxidative amination of aldehydes to furnish industrially important amides. The Royal Society of Chemistry 2014.
- Sharma,Sharma, Shivani
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p. 1292 - 1304
(2014/01/06)
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- Direct N-acylation of azoles via a metal-free catalyzed oxidative cross-coupling strategy
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The KI-catalyzed N-acylation of azoles via direct oxidative coupling of C-H and N-H bonds has been developed. It could be smoothly scaled up to gram synthesis of acyl azoles. The reaction occurred by the coupling of acyl radicals and azoles to form the acyl azole radical anion, followed by its further oxidation. This journal is the Partner Organisations 2014.
- Zhao, Jingjing,Li, Pan,Xia, Chungu,Li, Fuwei
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supporting information
p. 4751 - 4754
(2014/05/06)
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