- In vitro metabolism and interactions of pyridostigmine bromide, N,N-diethyl-m-toluamide, and permethrin in human plasma and liver microsomal enzymes
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1. The in vitro human plasma activity and liver microsomal metabolism of pyridostigmine bromide (PB), a prophylactic treatment against organophosphate nerve agent attack, N,N-diethyl-m-toluamide (DEET), an insect repellent, and permethrin, a pyrethroid insecticide, either alone or in combination were investigated. 2. The three chemicals disappeared from plasma in the following order: permethrin > PB > DEET. The combined incubation of DEET with either permethrin or PB had no effect on permethrin or PB. Binary incubation with permethrin decreased the metabolism of PB and its disappearance from plasma and binary incubation with PB decreased the metabolism of permethrin and its clearance from plasma. Incubation with PB and/or permethrin shortened the DEET terminal half-life in plasma. These agents behaved similarly when studied in liver microsomal assays. The combined incubation of DEET with PB or permethrin (alone or in combination) diminished DEET metabolism in microsomal systems. 3. The present study evidences that PB and permethrin are metabolized by both human plasma and liver microsomal enzymes and that DEET is mainly metabolized by liver oxidase enzymes. Combined exposure to test chemicals increases their neurotoxicity by impeding the body's ability to eliminate them because of the competition for detoxifying enzymes.
- Abu-Qare,Abou-Donia
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Read Online
- Nitrogen Atom Transfer Catalysis by Metallonitrene C?H Insertion: Photocatalytic Amidation of Aldehydes
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C?H amination and amidation by catalytic nitrene transfer are well-established and typically proceed via electrophilic attack of nitrenoid intermediates. In contrast, the insertion of (formal) terminal nitride ligands into C?H bonds is much less developed and catalytic nitrogen atom transfer remains unknown. We here report the synthesis of a formal terminal nitride complex of palladium. Photocrystallographic, magnetic, and computational characterization support the assignment as an authentic metallonitrene (Pd?N) with a diradical nitrogen ligand that is singly bonded to PdII. Despite the subvalent nitrene character, selective C?H insertion with aldehydes follows nucleophilic selectivity. Transamidation of the benzamide product is enabled by reaction with N3SiMe3. Based on these results, a photocatalytic protocol for aldehyde C?H trimethylsilylamidation was developed that exhibits inverted, nucleophilic selectivity as compared to typical nitrene transfer catalysis. This first example of catalytic C?H nitrogen atom transfer offers facile access to primary amides after deprotection.
- Schmidt-R?ntsch, Till,Verplancke, Hendrik,Lienert, Jonas N.,Demeshko, Serhiy,Otte, Matthias,Van Trieste, Gerard P.,Reid, Kaleb A.,Reibenspies, Joseph H.,Powers, David C.,Holthausen, Max C.,Schneider, Sven
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- Green and efficient Beckmann rearrangement by Cu(II) contained nano-silica triazine based dendrimer in water
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In this research, a Cu(II) contained nano-silica triazine based dendrimer was prepared, characterized, and utilized as a retrievable catalytic system (Cu(II)-TrDen@nSiO2) for green formation of primary amides in water at room temperature. The structure of nanoparticles was fully characterized by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), Fourier transform infrared spectroscopy (FT-IR), and thermogravimetry analysis (TGA). The results revealed that the nanoparticles have spherical morphology and an average size of around 40 nm. The analysis also illustrated that the copper nanoparticles had been successfully loaded on the nitrogen-rich dendritic structure with a uniform distribution. The inductively coupled plasma analysis showed that about 0.67 mmol/g of Cu was loaded on the Cu(II)-TrDen@nSiO2 support. Mild reaction conditions, excellent yields, environment-friendly synthesis, and easily prepared starting materials are the key features of the present method. The catalyst is easily removed from the reaction media using a simple filtration and can be re-used at least five times without any considerable loss of its catalytic activity.
- Bahreininejad, Mohammad Hasan,Moeinpour, Farid
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p. 893 - 901
(2021/01/12)
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- Half-Sandwich Iridium Complexes Based on β-Ketoamino Ligands: Preparation, Structure, and Catalytic Activity in Amide Synthesis
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A series of β-ketoamino-based N,O-chelate half-sandwich iridium complexes with the general formula [Cp*IrClL] have been prepared in good yields. These air-insensitive iridium complexes showed desirable catalytic activity in an amide preparation under mild conditions. A number of amides with diverse substituted groups were furnished in a one-pot reaction with good-to-excellent yields through an amidation reaction of NH2OH·HCl with aldehydes in the presence of these iridium(III) precursors. The excellent catalytic activity, mild reaction conditions, and broad substrate scope gave this type of iridium catalyst potential for use in industry. All of the obtained iridium complexes were well characterized by different spectroscopy techniques. The exact molecular structure of complex 3 has been confirmed by single-crystal X-ray analysis.
- Wang, Yang,Guo, Wen,Guan, Ai-Lin,Liu, Shuang,Yao, Zi-Jian
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p. 11514 - 11520
(2021/07/31)
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- Efficient nitriding reagent and application thereof
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The invention discloses an efficient nitriding reagent and application thereof, wherein the nitriding reagent comprises nitrogen oxide, an active agent, a reducing agent and an organic solvent. By applying the nitriding reagent, nitrogen-containing compounds such as amide, nitrile and the like can be produced, and the method is simple in condition, low in waste discharge amount and simple in reaction equipment.
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Paragraph 0324-0326
(2021/03/31)
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- Ru(ii)- And Ru(iv)-dmso complexes catalyze efficient and selective aqueous-phase nitrile hydration reactions under mild conditions
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New water-soluble ruthenium(ii)- and ruthenium(iv)-dmso complexes [RuCl2(dmso)2(NH3)(CH3CN)] (1), [RuCl2(dmso)3(CH3CN)] (2), and [RuCl2(dmso)3(NH3)]·PF6·Cl (3) have been synthesized and characterized using elemental analyses, IR, 1H and 31P NMR, and electronic absorption spectroscopy. The molecular structures of complexes 1-3 were determined crystallographically. The reactivity of complexes 1-3 has been tested for aqueous-phase nitrile hydration at 60 °C in air, and good efficiency and selectivity are shown for the corresponding amide derivatives. Best performance is achieved with complex 3. Amide conversions of 56-99% were obtained with a variety of aromatic, alkyl, and vinyl nitriles. The reaction tolerated hydroxyl, nitro, bromo, formyl, pyridyl, benzyl, alkyl, and olefinic functional groups. Amides were isolated by simple decantation from the aqueous-phase catalyst. A catalyst loading down to 0.0001 mol% was examined and turnover numbers as high as 990?000 were observed. The catalyst was stable for weeks in solution and could be reused more than seven times without significant loss in catalytic activity. The gram-scale reaction was also performed to produce the desired product in high yields. This journal is
- Dubey, Santosh Kumar,Kaur, Gurmeet,Rath, Nigam P.,Trivedi, Manoj
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p. 17339 - 17346
(2021/10/08)
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- Aerobic oxidation of primary amines to amides catalyzed by an annulated mesoionic carbene (MIC) stabilized Ru complex
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Catalytic aerobic oxidation of primary amines to the amides, using the precatalyst [Ru(COD)(L1)Br2] (1) bearing an annulated π-conjugated imidazo[1,2-a][1,8]naphthyridine-based mesoionic carbene ligand L1, is disclosed. This catalytic protocol is distinguished by its high activity and selectivity, wide substrate scope and modest reaction conditions. A variety of primary amines, RCH2NH2 (R = aliphatic, aromatic and heteroaromatic), are converted to the corresponding amides using ambient air as an oxidant in the presence of a sub-stoichiometric amount of KOtBu in tBuOH. A set of control experiments, Hammett relationships, kinetic studies and DFT calculations are undertaken to divulge mechanistic details of the amine oxidation using 1. The catalytic reaction involves abstraction of two amine protons and two benzylic hydrogen atoms of the metal-bound primary amine by the oxo and hydroxo ligands, respectively. A β-hydride transfer step for the benzylic C-H bond cleavage is not supported by Hammett studies. The nitrile generated by the catalytic oxidation undergoes hydration to afford the amide as the final product. This journal is
- Yadav, Suman,Reshi, Noor U Din,Pal, Saikat,Bera, Jitendra K.
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p. 7018 - 7028
(2021/11/17)
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- Visible light-mediated synthesis of amides from carboxylic acids and amine-boranes
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Here, a photocatalytic deoxygenative amidation protocol using readily available amine-boranes and carboxylic acids is described. This approach features mild conditions, moderate-to-good yields, easy scale-up, and up to 62 examples of functionalized amides with diverse substituents. The synthetic robustness of this method was also demonstrated by its application in the late-stage functionalization of several pharmaceutical molecules.
- Chen, Xuenian,Kang, Jia-Xin,Ma, Yan-Na,Miao, Yu-Qi
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supporting information
p. 3595 - 3599
(2021/06/06)
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- Cu(II)-promoted oxidative C-N bond cleavage of N-benzoylamino acids to primary aryl amides
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A novel protocol for CuCl2-promoted oxidative C-N bond cleavage of N-benzoyl amino acids was developed. It is the first example of using accessible amino acid as an ammonia synthetic equivalent for the synthesis of primary aryl amides via CuCl2-promoted oxidative C-N bond cleavage reaction. The present protocol shows excellent functional group tolerance and provides an alternative method for the synthetic of primary aryl amides in 84-96% yields.
- Zhou, Liandi,Liu, Wei,Zhao, Yongli,Chen, Junmin
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- Cu(II)–metformin immobilized on graphene oxide: an efficient and recyclable catalyst for the Beckmann rearrangement
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Abstract: In this study, for the first time, the copper(II) nanoparticles (NPs) have been immobilized on metformin-functionalized graphene oxide and then its catalytic applications have been investigated in synthesis of amides from aldoximes (Beckmann rearrangement). The chemical structure of prepared catalyst has been characterized by various analyses like FT-IR, TGA, TEM, SEM, EDX, and ICP. All analyses confirm the successful and stable immobilization of copper NPs on functionalized graphene oxide. This synthesized heterogeneous nanocatalyst showed excellent catalytic activity with high product yields and short reaction times. Also, the suggested catalyst could be recycled ten times without a drastic decrease in its catalytic activity. Graphic abstract: [Figure not available: see fulltext.].
- Solaiman Hamed, Ahmed,Mohammad Ali, Ehab
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p. 701 - 714
(2019/11/03)
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- Half-Sandwich Iridium Complexes for the One-Pot Synthesis of Amides: Preparation, Structure, and Diverse Catalytic Activity
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Several types of air-stable N,O-coordinate half-sandwich iridium complexes containing Schiff base ligands with the general formula [Cp*IrClL] were synthesized in good yields. These stable iridium complexes displayed a good catalytic efficiency in amide synthesis. A variety of amides with different substituents were obtained in a one-pot procedure with excellent yields and high selectivities through the amidation of aldehydes with NH2OHHCl and nitrile hydration under the catalysis of complexes 1-4. The excellent and diverse catalytic activity, mild conditions, broad substance scope, and environmentally friendly solvent make this system potentially applicable in industrial production. Half-sandwich iridium complexes 1-4 were characterized by NMR, elemental analysis, and IR techniques. Molecular structures of complexes 2 and 3 were confirmed by single-crystal X-ray analysis.
- Fan, Xiao-Nan,Deng, Wei,Liu, Zhen-Jiang,Yao, Zi-Jian
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p. 16582 - 16590
(2020/11/13)
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- Nitromethane as a nitrogen donor in Schmidt-type formation of amides and nitriles
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The Schmidt reaction has been an efficient and widely used synthetic approach to amides and nitriles since its discovery in 1923. However, its application often entails the use of volatile, potentially explosive, and highly toxic azide reagents. Here, we report a sequence whereby triflic anhydride and formic and acetic acids activate the bulk chemical nitromethane to serve as a nitrogen donor in place of azides in Schmidt-like reactions. This protocol further expands the substrate scope to alkynes and simple alkyl benzenes for the preparation of amides and nitriles.
- Jiao, Ning,Liu, Jianzhong,Qiu, Xu,Song, Song,Wei, Jialiang,Wen, Xiaojin,Zhang, Cheng,Zhang, Ziyao
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supporting information
p. 281 - 285
(2020/01/28)
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- INHIBITORS OF α-AMINO-β-CARBOXYMUCONIC ACID SEMIALDEHYDE DECARBOXYLASE
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The present disclosure discloses compounds capable of modulating the activity of α-amino-β-carboxymuconic acid semialdehyde decarboxylase (ACMSD), which are useful for the prevention and/or the treatment of diseases and disorders associated with defects in NAD+ biosynthesis, e.g., metabolic disorders, neurodegenerative diseases, chronic inflammatory diseases, kidney diseases, and diseases associated with ageing. The present application also discloses pharmaceutical compositions comprising said compounds and the use of such compounds as a medicament.
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Paragraph 00479
(2020/06/10)
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- Fragment based drug design and diversity-oriented synthesis of carboxylic acid isosteres
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The medicinal chemist toolbox is plenty of (bio)isosteres when looking for a carboxylic acid replacement. However, systematic assessment of acid surrogates is often time consuming and expensive, while prediction of both physicochemical properties (logP and logD) as well as acidity would be desirable at early discovery stages for a better analog design. Herein in this work, to enable decision making on a project, we have synthesized by employing a Diversity-Oriented Synthetic (DOS) methodology, a small library of molecular fragments endowed with acidic properties. By combining in-silico and experimental methodologies these compounds were chemically characterized and, particularly, with the aim to know their physicochemical properties, the aqueous ionization constants (pKa), partition coefficients logD and logP of each fragment was firstly estimated by using molecular modeling studies and then validated by experimental determinations. A face to face comparison between data and the corresponding carboxylic acid might help medicinal chemists in finding the best replacement to be used. Finally, in the framework of Fragment Based Drug Design (FBDD) the small library of fragments obtained with our approach showed good versatility both in synthetic and physico-chemical properties.
- Alunno, Manuel,Camaioni, Emidio,Carotti, Andrea,Ferri, Martina,Greco, Francesco Antonio,Liscio, Paride,Macchiarulo, Antonio,Mammoli, Andrea,Saluti, Giorgio,Sardella, Roccaldo
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- Arene-ruthenium(II)-phosphine complexes: Green catalysts for hydration of nitriles under mild conditions
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Three new arene-ruthenium(II) complexes were prepared by treating [{RuCl(μ-Cl)(η6-arene)}2] (η6-arene = p-cymene) dimer with tri(2-furyl)phosphine (PFu3) and 1,3,5-triaza-7-phosphaadamantane (PTA), respectively to obtain [RuCl2(η6-arene)PFu3] [Ru]-1, [RuCl(η6-arene)(PFu3)(PTA)]BF4 [Ru]-2 and [RuCl(η6-arene)(PFu3)2]BF4 [Ru]-3. All the complexes were structurally identified using analytical and spectroscopic methods including single-crystal X-ray studies. The effectiveness of resulting complexes as potential homogeneous catalysts for selective hydration of different nitriles into corresponding amides in aqueous medium and air atmosphere was explored. There was a remarkable difference in catalytic activity of the catalysts depending on the nature and number of phosphorus-donor ligands and sites available for catalysis. Experimental studies performed using structural analogues of efficient catalyst concluded a structural-activity relationship for the higher catalytic activity of [Ru]-1, being able to convert huge variety of aromatic, heteroaromatic and aliphatic nitriles. The use of eco-friendly water as a solvent, open atmosphere and avoidance of any organic solvent during the catalytic reactions prove the reported process to be truly green and sustainable.
- Vyas, Komal M.,Mandal, Poulami,Singh, Rinky,Mobin, Shaikh M.,Mukhopadhyay, Suman
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- Aerobic oxidation of primary benzylic amines to amides and nitriles catalyzed by ruthenium carbonyl clusters carrying N,O-bidentate ligands
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Four trinuclear ruthenium carbonyl clusters, (6-BrPyCHRO)2Ru3(CO)8 (R = 4-OCH3C6H4, 1a; R = 4-BrC6H4, 1b) and (2-OC6H4-HCN-C6H4R)2Ru3(CO)8 (R = 4-OCH3, 2a; R = 4-Br, 2b), were synthesized from the reactions of Ru3(CO)12 with the corresponding N,O-bidentate ligands (two pyridyl alcohols and two Schiff bases) respectively in a ratio of 1:2. Three new complexes 1b, 2a and 2b have been fully characterized by elemental analysis, FT-IR, NMR and X-ray crystallography. The catalytic activity of these ruthenium complexes for the aerobic oxidation of primary benzylic amines to amides and nitriles in the presence of t-BuOK was investigated, of which the Schiff base complex 2a was found to exhibit the highest activity.
- Dong, Qing,Han, Zhangang,Hao, Zhiqiang,Li, Ying,Lin, Jin,Lu, Guo-Liang,Meng, Lizhen,Yan, Xinlong
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p. 3480 - 3487
(2020/04/02)
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- Supported palladium catalyzed aminocarbonylation of aryl iodides employing bench-stable CO and NH3surrogates
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A simple, efficient and phosphine free protocol for carbonylative synthesis of primary aromatic amides under polystyrene supported palladium (Pd?PS) nanoparticle (NP) catalyzed conditions has been demonstrated. Herein, instead of using two toxic and difficult to handle gases simultaneously, we have employed the solid, economical, bench stable oxalic acid as the CO source and ammonium carbamate as the NH3source in a single pot reaction. For the first time, we have applied two non-gaseous surrogates simultaneously under heterogeneous catalyst (Pd?PS) conditions for the synthesis of primary amides using an easy to handle double-vial (DV) system. The developed strategy showed a good functional group tolerance towards a wide range of aryl iodides and afforded primary aromatic amides in good yields. The Pd?PS catalyst was easy to separate and can be recycled up to four consecutive runs with small loss in catalytic activity. We have successfully extended the scope of the methodology to the synthesis of isoindole-1,3-diones from 1,2-dihalobenzene, 2-halobenzoates and 2-halobenzoic acid following double and single carbonylative cyclization approaches.
- Bains, Rohit,Das, Pralay,Kumar, Ajay,Ram, Shankar,Shaifali,Sheetal
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supporting information
p. 7193 - 7200
(2020/10/02)
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- Pyridine-Enabled C-N Bond Activation for the Rapid Construction of Amides and 4-Pyridylglyoxamides by Cooperative Palladium/Copper Catalysis
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A pyridine-enabled C-N bond activation of peptidomimetics employing cooperative palladium/copper catalysis in water is developed. Diverse amides and 4-pyridylglyoxamides are simultaneously synthesized through two steps from commercially available materials in a rapid, environmentally friendly, and high atom-economical manner.
- Song, Liangliang,Claessen, Sander,Van Der Eycken, Erik V.
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p. 8045 - 8054
(2020/07/15)
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- Base-Mediated Amination of Alcohols Using Amidines
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Novel and efficient base-mediated N-alkylation and amidation of amidines with alcohols have been developed, which can be carried out in one-pot reaction conditions, which allows for the synthesis of a wide range of N-alkyl amines and free amides in good to excellent yields with high atom economy. In contrast to borrowing hydrogen/hydrogen autotransfer or oxidative-type N-alkylation reactions, in which alcohols are activated by transition-metal-catalyzed or oxidative aerobic dehydrogenation, the use of amidines provides an effective surrogate of amines. This circumvents the inherent necessity in N-alkylation of an oxidant or a catalyst to be stabilized by ligands.
- Chen, Jianbin,Fang, Yanchen,Jia, Xiaofei,Jiang, Shaohua,Li, Zehua,Liang, Zuyu,Lu, Fenghong,Qi, Shuo,Ren, Chaoyu,Yu, Shuangming,Zhang, Chunyan,Zhang, Guoying,Zhang, Sheng
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p. 7728 - 7738
(2020/07/15)
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- Transamidation for the Synthesis of Primary Amides at Room Temperature
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Various primary amides have been synthesized using the transamidation of various tertiary amides under metal-free and mild reaction conditions. When (NH4)2CO3 reacts with a tertiary amide bearing an N-electron-withdrawing substituent, such as sulfonyl and diacyl, in DMSO at 25 °C, the desired primary amide product is formed in good yield with good funcctional group tolerance. In addition, N-tosylated lactam derivatives afforded their corresponding N-tosylamido alkyl amide products via a ring opening reaction.
- Chen, Jiajia,Lee, Sunwoo,Xia, Yuanzhi
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supporting information
(2020/05/05)
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- Aqueous-Phase Nitrile Hydration Catalyzed by an In Situ Generated Air-Stable Ruthenium Catalyst
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RuCl2(PTA)4 (PTA=1,3,5-triaza-7-phosphaadamantane) is an active, recyclable, air-stable, aqueous-phase nitrile hydration catalyst. The development of an in situ generated aqueous-phase nitrile hydration catalyst (RuCl3?3 H2O+6 equivalents PTA) is reported. The activity of the in situ catalyst is comparable to RuCl2(PTA)4. The effects of [PTA] on the activity of the reaction were investigated: the catalytic activity, in general, increases as the pH goes up, which shows a positive correlation with [PTA]. The pH effects were further explored for both the in situ and RuCl2(PTA)4 catalyzed reaction in phosphate buffer solutions with particular attention given to pH 6.8 buffer. Increased catalytic activity was observed at pH 6.8 versus water for both systems with turnover frequency (TOF) up to 135 h?1 observed for RuCl2(PTA)4 and 64 h?1 for the in situ catalyst. Catalyst loading down to 0.001 mol % was examined with turnover numbers as high as 22 000 reported. Similar to the preformed catalyst, RuCl2(PTA)4, the in situ catalyst could be recycled more than five times without significant loss of activity from either water or pH 6.8 buffer.
- Ounkham, Whalmany L.,Weeden, Jason A.,Frost, Brian J.
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supporting information
p. 10013 - 10020
(2019/07/15)
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- Activation of nitriles by silver(I) N-heterocyclic carbenes: An efficient on-water synthesis of primary amides
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A first example of silver(I) N-heterocyclic carbene (Ag(I)-NHC) catalyzed on-water synthesis of primary amides by hydration of nitriles under mild reaction conditions is described. This organometallic catalytic system has excellent tolerance for various homo-aromatic, hetero-aromatic and aliphatic nitriles to afford primary amides in good yields in neat water.
- Thirukovela, Narasimha Swamy,Balaboina, Ramesh,Kankala, Shravankumar,Vadde, Ravindhar,Vasam, Chandra Sekhar
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supporting information
p. 2637 - 2641
(2019/03/21)
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- Trash to treasure: Eco-friendly and practical synthesis of amides by nitriles hydrolysis in WepPA
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The hydration of nitriles to amides in a water extract of pomelo peel ash (WEPPA) was realized with moderate to excellent yields without using external transition metals, bases or organic solvents. This reaction features a broad substrate scope, wide functional group tolerance, prominent chemoselectivity, and good reusability. Notably, a magnification experiment in this bio-based solvent at 100 mmol further demonstrated its practicability.
- Sun, Yajun,Jin, Weiwei,Liu, Chenjiang
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supporting information
(2019/11/11)
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- Selectivity-tunable amine aerobic oxidation catalysed by metal-free N,O-doped carbons
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Herein, we present a series of N,O-doped mesoporous carbons obtained at different pyrolysis temperatures as the first metal-free catalysts which successfully switch between imine and nitrile products for amine oxidation. Systematic characterization studies and control experiments revealed that the C-O group on the surface could function as a catalytically active site for nitrile synthesis and the N-doping environment was essential.
- Li, Yingguang,Shang, Sensen,Wang, Lianyue,Lv, Ying,Niu, Jingyang,Gao, Shuang
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supporting information
p. 12251 - 12254
(2019/10/21)
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- [VO(PS-BBMA)](SO4) catalyzed Α-oxygenation of benzylamines to amides in solvent free condition
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Polymer anchored [VO(PS-BBMA)]SO4 and unsupported [VO(BBMA)]SO4 catalysts were synthesized and characterized by elemental analyses, FT-IR, ESR, UV–vis diffuse reflectance spectroscopy (DRS), thermogravimetric analysis (TGA), and vibrating sample magnetometry (VSM). A protocol for the synthesis of benzamides from benzylamine has been developed using [VO(PS-BBMA]SO4 as an effective catalyst under solvent free conditions in presence of H2O2. The reactions provide good yields of the corresponding amide products with substrate scope and excellent functional group compatibility. The developed catalyst can be facilely recovered, heterogeneous, compared with unsupported analogue and reused six times without significant decrease in its activity.
- Renuka,Gayathri
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- Method for preparing derivatives of benzamide under microwave condition in aqueous phase
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The invention discloses a method for preparing derivatives of benzamide under a microwave condition in an aqueous phase. A coupling reaction is carried out between substituted benzoic acid and amine under the microwave condition in the aqueous phase. The method for preparing the derivatives of benzamide is environmentally friendly, easy and convenient to operate, safe, low in cost and efficient. Compared with the prior art, the method can be applicable to a large number of functional groups, is high in yield, produces fewer by-products, and further is easy to operate, safe, low in cost and environmentally friendly. A formula is shown in the description.
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Paragraph 0018; 0082
(2019/03/28)
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- Novel design of recyclable copper(II) complex supported on magnetic nanoparticles as active catalyst for Beckmann rearrangement in poly(ethylene glycol)
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Copper complex-functionalized magnetic core–shell nanoparticles (Fe3O4@SiO2-Lig-Cu) were prepared and characterized using various techniques. The activity of the new catalyst was tested for the Beckmann rearrangement. The reaction conditions allow for the conversion of a wide variety of aldoximes, including aromatic and heterocyclic ones, to amides in good to excellent yields. High efficiency, mild reaction conditions, easy work-up, use of poly(ethylene glycol) as a green medium and simple purification of products are important advantages of this system. Moreover, the eco-friendly heterogeneous nanocatalyst could be easily recovered from the reaction mixture using an external magnet and reused several times.
- Keyhaniyan, Mahdi,Shiri, Ali,Eshghi, Hossein,Khojastehnezhad, Amir
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- Metal-Free Nitrogen- and Boron-Codoped Mesoporous Carbons for Primary Amides Synthesis from Primary Alcohols via Direct Oxidative Dehydrogenation
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Metal-free catalysts show environmental friendliness and cost-effectiveness, as well as less susceptibility to poisoning over metal and metal oxide catalysts. In this respect, we present the synthesis and characterization of metal-free mesoporous nitrogen- and boron-codoped nanocarbon (meso-N,B/C), which exhibits good catalytic performance with conversion of 89% and selectivity of 83% toward amide synthesis from primary alcohols using NH4OAc as an ammonia resource under an oxygen atmosphere. The facile codoping synthetic strategy was executed by pyrolysis of nitrogen-enriched ligand 4,5-diazafluorene-9-one azine (DAA) and H3BO3 as a nitrogen and boron content modulator, respectively. Significantly, control experiments revealed that the reaction proceeded through direct oxidative dehydrogenation of hemiaminal after aldehyde-ammonia condensation, which was remarkably different from that in the previous literature. Density functional theory (DFT) calculations further demonstrate that the selective preference for benzamide largely benefits from the strong adsorption and enhanced activity of oxygen molecules via the interaction with a B atom doped in the catalyst. The active sites in the meso-N,B/C catalyst are proposed to be B atom bonded with N within the graphitic carbon sheets. This founding opens up avenues for the development of modified carbon materials on metal-free catalysis.
- Shang, Sensen,Chen, Pei-Pei,Wang, Lianyue,Lv, Ying,Li, Wei-Xue,Gao, Shuang
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p. 9936 - 9944
(2018/10/15)
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- Phosphinous Acid-Assisted Hydration of Nitriles: Understanding the Controversial Reactivity of Osmium and Ruthenium Catalysts
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The synthesis and catalytic behavior of the osmium(II) complexes [OsCl2(η6-p-cymene)(PR2OH)] [R=Me (2 a), Ph (2 b), OMe (2 c), OPh (2 d)] in nitrile hydration reactions is presented. Among them, the best catalytic results were obtained with the phosphinous acid derivative [OsCl2(η6-p-cymene)(PMe2OH)] (2 a), which selectively provided the desired primary amides in excellent yields and short times at 80 °C, employing directly water as solvent, and without the assistance of any basic additive (TOF values up to 200 h?1). The process was successful with aromatic, heteroaromatic, aliphatic, and α,β-unsaturated organonitriles, and showed a high functional group tolerance. Indeed, complex 2 a represents the most active and versatile osmium-based catalyst for the hydration of nitriles reported so far in the literature. In addition, it exhibits a catalytic performance similar to that of its ruthenium analogue [RuCl2(η6-p-cymene)(PMe2OH)] (4). However, when compared to 4, the osmium complex 2 a turned out to be faster in the hydration of less-reactive aliphatic nitriles, whereas the opposite trend was generally observed with aromatic substrates. DFT calculations suggest that these differences in reactivity are mainly related to the ring strain associated with the key intermediate in the catalytic cycle, that is, a five-membered metallacyclic species generated by intramolecular addition of the hydroxyl group of the phosphinous acid ligand to the metal-coordinated nitrile.
- González-Fernández, Rebeca,Crochet, Pascale,Cadierno, Victorio,Menéndez, M. Isabel,López, Ramón
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p. 15210 - 15221
(2017/10/12)
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- Remote meta-C–H Cyanation of Arenes Enabled by a Pyrimidine-Based Auxiliary
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An easily removable pyrimidine-based auxiliary has been employed for the remote meta-C?H cyanation of arenes. The scope of this Pd-catalyzed cyanation reaction using copper(I) cyanide as the cyanating agent was demonstrated with benzylsilanes, benzylsulfonates, benzylphophonates, phenethylsulfonates, and phenethyl ether derivatives. The method was utilized for the synthesis of pharmaceutically valuable precursors.
- Bag, Sukdev,Jayarajan, Ramasamy,Dutta, Uttam,Chowdhury, Rajdip,Mondal, Rahul,Maiti, Debabrata
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supporting information
p. 12538 - 12542
(2017/09/12)
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- Half-sandwich ruthenium complexes with oxygen–nitrogen mixed ligands as efficient catalysts for nitrile hydration reaction
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Three ruthenium(II) p-cymene complexes containing oxygen–nitrogen mixed ligands [Ru(p-cymene)LCl] [HL = 2-(4,5-dihydrooxazol-2-yl)phenol (2a); HL = 2-(4,5-dihydrothiazol-2-yl)phenol (2b); HL = 2-(5,6-dihydro-4H-1,3-oxazin-2-yl)phenol (2c)] have been synthesized and characterized. All half-sandwich ruthenium complexes were fully characterized by 1H and 13C NMR spectra, elemental analyses and infrared spectrometry. The molecular structure of ruthenium complex 2c was further confirmed by single-crystal X-ray diffraction methods. Furthermore, these half-sandwich ruthenium complexes are active catalysts for the hydration of nitriles to amides in the presence of sodium hydroxide in isopropanol.
- Jia, Wei-Guo,Ling, Shuo,Fang, Shen-Jie,Sheng, En-Hong
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- Efficient Hydration of Nitriles Promoted by Gallic Acid Derived from Renewable Bioresources
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An efficient gallic acid promoted nitriles hydration at room temperature with ethanol/water as a solvent has been developed. The present protocol offers a wide range of amides in moderate to good yields. Moreover, galla chinensis extract can serve as the promoter to perform the hydration, which also shows the potential utilization of natural feedstocks.
- Deng, Tao,Wang, Cheng-Zhang
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p. 1349 - 1353
(2017/04/14)
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- A selective hydration of nitriles catalysed by a Pd(OAc)2-based system in water
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In situ formation of a [Pd(OAc)2bipy] (bipy = 2,2′-bipyridyl) complex in water selectively catalyses the hydration of a wide range of organonitriles at 70 °C. Catalyst loadings of 5 mol% afford primary amide products in excellent yields in the absence of hydration-promoting additives such as oximes and hydroxylamines.
- Sanz Sharley, Daniel D.,Williams, Jonathan M.J.
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supporting information
p. 4090 - 4093
(2017/09/27)
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- Mixed-valence μ3-oxo-centered triruthenium cluster [Ru3(II,III,III)(μ3-O)(μ-CH3CO2)6(H2O)3]·2H2O: Synthesis, structural characterization, valence-state delocalization and catalytic behavior
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The oxo-centered, trinuclear, mixed valence [Ru3(II,III,III)O(CH3CO2)6(H2O)3]·2H2O (2) acetate complex has been prepared with high yield through reduction of [Ru3(III,III,III)O(CH3CO2)6(CH3OH)3]·CH3CO2precursor compound in presence of muccic acid under hydrothermal conditions. The crystalline trinuclear oxo-cluster has been obtained as crystalline powder and characterized by single-crystal and powder X-ray diffraction, elemental analysis, SEM, TGA, IR spectroscopy. Complex 2 composes of μ3-oxocentered trinuclear ruthenium array and exhibits the oxidation state delocalization between three Ru atoms at 293 K. Accurate single-crystal analysis along with valence bond calculations reveal trapped-valence state delocalization at room temperature, whereas three-site relaxation occurs at 100 K leading to Ru(II) and Ru2(III) formal states. Moreover, the mixed valence of RuIIRu2IIIunit in compound 2 has been confirmed by XANES spectroscopy. The catalytic behavior of oxo-centered triruthenium complex 2 has been examined in hydration of nitriles and isomerization of allylic alcohols reactions both realized in aqueous media.
- Dikhtiarenko, Alla,Khainakov, Sergei,García, José R.,Gimeno, José
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p. 107 - 116
(2016/11/19)
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- A Convenient Palladium-Catalyzed Aminocarbonylation of Aryl Iodides to Primary Amides under Gas-Free Conditions
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A convenient procedure for the synthesis of aromatic primary amides through palladium-catalyzed aminocarbonylation of aryl iodides has been developed. With ammonium hydrogen carbonate as the solid nitrogen source and formic acid as the liquid CO source, a variety of primary amides were obtained in moderate to excellent yields under gas-free conditions.
- Qi, Xinxin,Ai, Han-Jun,Cai, Chuang-Xu,Peng, Jin-Bao,Ying, Jun,Wu, Xiao-Feng
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supporting information
p. 7222 - 7225
(2018/01/02)
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- 1,3-Dibromo-5,5-dimethylhydantoin mediated oxidative amidation of terminal alkenes in water
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A variety of terminal alkenes were converted to the corresponding amides in yields of 25 to 86% in water via treatment with 1,3-dibromo-5,5-dimethylhydantoin, followed by reaction with molecular iodine and aq. NH3 (or amine) in one pot. This metal- and organic solvent-free protocol is not only suitable for styrene derivatives, but also, for the first time, works well on terminal aliphatic alkenes.
- Ma, Chunhua,Fan, Guojie,Wu, Ping,Li, Zhi,Zhou, Yang,Ding, Qingjie,Zhang, Wei
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p. 9889 - 9894
(2017/12/12)
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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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- Dithioester-enabled chemodivergent synthesis of acids, amides and isothiazoles via C[sbnd]C bond cleavage and C[sbnd]O/C[sbnd]N/C[sbnd]S bond formations under metal- and catalyst-free conditions
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An operationally simple and user-friendly process to access privileged scaffolds such as acids, amides and isothiazoles has been devised employing β-ketodithioesters for the first time. Remarkably, the new protocol involves combination of C[sbnd]C bond cl
- Soni, Sonam,Koley, Suvajit,Singh, Maya Shankar
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supporting information
p. 2512 - 2516
(2017/05/31)
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- Cu-catalyzed aerobic oxidative C-CN bond cleavage of benzyl cyanide for the synthesis of primary amides
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An efficient method via copper-catalyzed aerobic oxidative amidation of benzyl cyanide for primary amides is successfully developed. Using readily available NH4Cl as a nitrogen source and Cu/O2 as a catalytic oxidation system offers new opportunities for C-CN bond cleavage and primary amide bond formation.
- Chen, Xiuling,Peng, Yanhong,Li, Yan,Wu, Minghu,Guo, Haibing,Wang, Jian,Sun, Shaofa
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p. 18588 - 18591
(2017/04/04)
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- Transfer Hydro-dehalogenation of Organic Halides Catalyzed by Ruthenium(II) Complex
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A simple and efficient Ru(II)-catalyzed transfer hydro-dehalogenation of organic halides using 2-propanol solvent as the hydride source was reported. This methodology is applicable for hydro-dehalogenation of a variety of aromatic halides and α-haloesters and amides without additional ligand, and quantitative yields were achieved in many cases. The potential synthetic application of this method was demonstrated by efficient gram-scale transformation with catalyst loading as low as 0.5 mol %.
- You, Tingjie,Wang, Zhenrong,Chen, Jiajia,Xia, Yuanzhi
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p. 1340 - 1346
(2017/02/10)
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- Aminocarbonylation of Aryl Halides to Produce Primary Amides by Using NH4HCO3 Dually as Ammonia Surrogate and Base
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An efficient and clean protocol was developed for rapid production of primary aromatic amides by aminocarbonylation with NH4HCO3. Without addition of auxiliary base, the use of solid and cheap NH4HCO3 dually as ammonia surrogate and base not only promoted aminocarbonylation over subsequent dehydration and hydrolysis of amides owing to its weak basicity, and it also made the reaction manipulation clean and simplified without the presence of stinky NH3 or organic amines. The Xantphos ligand with relatively intensive π-acceptor character (1J31P–77Se=758 Hz) and wide natural bite angle (βn=111°) was found to be indispensable for the high efficiency of this reaction.
- Wang, Dong-Liang,Liu, Huan,Yang, Da,Wang, Peng,Lu, Yong,Liu, Ye
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p. 4206 - 4211
(2017/12/02)
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- Adenylation Activity of Carboxylic Acid Reductases Enables the Synthesis of Amides
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Carboxylic acid reductases (CARs) catalyze the reduction of a broad range of carboxylic acids to aldehydes using the cofactors adenosine triphosphate and nicotinamide adenine dinucleotide phosphate, and have become attractive biocatalysts for organic synthesis. Mechanistic understanding of CARs was used to expand reaction scope, generating biocatalysts for amide bond formation from carboxylic acid and amine. CARs demonstrated amidation activity for various acids and amines. Optimization of reaction conditions, with respect to pH and temperature, allowed for the synthesis of the anticonvulsant ilepcimide with up to 96 % conversion. Mechanistic studies using site-directed mutagenesis suggest that, following initial enzymatic adenylation of substrates, amidation of the carboxylic acid proceeds by direct reaction of the acyl adenylate with amine nucleophiles.
- Wood, Alexander J. L.,Weise, Nicholas J.,Frampton, Joseph D.,Dunstan, Mark S.,Hollas, Michael A.,Derrington, Sasha R.,Lloyd, Richard C.,Quaglia, Daniela,Parmeggiani, Fabio,Leys, David,Turner, Nicholas J.,Flitsch, Sabine L.
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supporting information
p. 14498 - 14501
(2017/10/18)
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- Highly efficient synthesis of primary amides: Via aldoximes rearrangement in water under air atmosphere catalyzed by an ionic ruthenium pincer complex
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The transformation of aldoximes to primary amides has been evaluated using pincer ruthenium complexes a-c, among which the ionic Ru catalyst a proved to be the most efficient in water under air atmosphere. A variety of (hetero)arene aldoximes proceeded smoothly to afford amides in high yields with good functional group compatibilities. Furthermore, a direct synthetic route of amides from aldehydes, hydroxylamine hydrochloride and sodium carbonate was also described with broad substrates including conjugated and aliphatic aldehydes. This protocol is operationally simple and proceeds with a low catalyst loading (0.5 mol%).
- Yang, Fa-Liu,Zhu, Xinju,Rao, Dun-Kang,Cao, Xiao-Niu,Li, Ke,Xu, Yan,Hao, Xin-Qi,Song, Mao-Ping
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p. 37093 - 37098
(2016/05/24)
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- Synthesis and catalytic applications of ruthenium(ii)-phosphino-oxime complexes
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In this work, the preparation of the first ruthenium complexes containing a phosphino-oxime ligand is presented. Thus, the reaction of cis-[RuCl2(DMSO)4] (3) with 2.4 equivalents of 2-Ph2PC6H4CH=NOH (1) in refluxing THF led to the clean formation of the octahedral ruthenium(ii) derivative cis,cis,trans-[RuCl2{κ2-(P,N)-2-Ph2PC6H4CH=NOH}2] (5), whose structure was unambiguously confirmed by means of a single-crystal X-ray diffraction study. Complex 5 could also be synthesized from the reaction of the dimer [{RuCl(μ-Cl)(η6-p-cymene)}2] (4) with an excess of 1 in refluxing toluene. Treatment of 4 with 2 equivalents of 1, in CH2Cl2 at r.t., allowed also the preparation of the half-sandwich Ru(ii) derivative [RuCl{κ2-(P,N)-2-Ph2PC6H4CH=NOH}(η6-p-cymene)][PF6] (6). In addition, complexes 5 and 6 proved to be active catalysts for the rearrangement of aldoximes to primary amides, as well as for the α-alkylation/reduction of acetophenones with primary alcohols, with the former showing the best performances in both processes.
- Francos, Javier,Menéndez-Rodríguez, Lucía,Tomás-Mendivil, Eder,Crochet, Pascale,Cadierno, Victorio
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p. 39044 - 39052
(2016/06/01)
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- A mild hydration of nitriles catalysed by copper(ii) acetate
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A simple, mild and general procedure for the hydration of nitriles to amides using copper as catalyst and promoted by N,N-diethylhydroxylamine is described. The reaction can be conducted in water at low temperature in short reaction times. This new procedure allows amides to be obtained from a wide range of substrates in excellent yields.
- Marcé, Patricia,Lynch, James,Blacker, A. John,Williams, Jonathan M. J.
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supporting information
p. 1436 - 1438
(2016/01/25)
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- Clean synthesis of primary to tertiary carboxamides by CsOH-catalyzed aminolysis of nitriles in water
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Using CsOH as the only catalyst and utilizing its "cesium effect", a clean synthesis of a wide range of primary, secondary, and tertiary carboxamides was achieved by aminolysis reactions of nitriles with ammonia, primary, or secondary amines in water. Studies on the control reactions revealed that the reactions with ammonia most probably proceed via an aminolysis path by the initial addition of ammonia to Cs-activated nitriles to form unsubstituted amidine intermediates, while the reactions with primary or secondary amines may proceed via a hydration/transamidation path by the initial hydration of the Cs-activated nitriles to form primary carboxamide intermediates followed by their transamidation with amines through the formation of substituted amidine intermediates.
- Li, Yang,Chen, Haonan,Liu, Jianping,Wan, Xujun,Xu, Qing
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supporting information
p. 4865 - 4870
(2016/10/06)
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- Visible Light-Induced Iodine-Catalyzed Transformation of Terminal Alkynes to Primary Amides via C≡C Bond Cleavage under Aqueous Conditions
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The visible light-induced iodine-catalyzed oxidative cleavage of the C≡C bond for transforming terminal alkynes into primary amides in the presence of ammonia under aqueous conditions is described. This metal-free protocol which ensued via initial hydroamination of the acetylene bond followed by liberation of diiodomethane (CH2I2) was found to be applicable to aromatic, heteroaromatic and aliphatic alkynes.
- Dighe, Shashikant U.,Batra, Sanjay
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supporting information
p. 500 - 505
(2016/02/12)
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- Synthesis and antitumor activity of novel N-benzoyl-N'-substituted pyrimidinyl (thio)semicarbazide derivatives
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A series of substituted pyrimidinyl (thio)semicarbazide derivatives were designed and synthesized. The antitumor results showed that the activity of thiosemicarbazide compounds (series II) was generally higher than that of the corresponding semicarbazide derivatives (series I). Among them, IIk displayed higher cytotoxicity against HL-60, BGC-823 and Bel-7402 than that of adriamycin and exhibited broad in vitro cytotoxicity against 13 human tumor cell lines. Meanwhile, the cytotoxic selectivity and anti-multidrug resistance were evaluated, and IIk exhibited selective cytotoxicity against cancer cells in comparison to human normal cells and had significant anti-multidrug resistance capability. The bioassay results showed that IIk showed great promise as a potent lead compound for further antitumor discovery.
- Song, Gaopeng,Li, Jianzuo,Tian, Hao,Li, Yasheng,Hu, Dekun,Li, Ying,Cui, Zining
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p. 329 - 334
(2016/04/04)
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- Design, synthesis and fungicidal activity of N-substituted benzoyl-1,2,3,4-tetrahydroquinolyl-1-carboxamide
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To find a new lead compound with high biological activity, a series of N-substituted benzoyl-1,2,3,4-tetrahydroquinolyl-1-carboxamide were designed using linking active substructures method. The target compounds were synthesized from substituted benzoic acid by four steps and their structures were confirmed by 1H NMR, IR spectrum and elemental analysis. The in vitro bioassay results indicated that some target compounds exhibited excellent fungicidal activities, and the position of the substituents played an important role in fungicidal activities. Especially, compound 5n, exhibited better fungicidal activities than the commercial fungicide flutolanil against two tested fungi Valsa Mali and Sclerotinia sclerotiorum, with EC50 values of 3.44 and 2.63 mg/L, respectively. And it also displayed good in vivo fungicidal activity against S. sclerotiorum with the EC50 value of 29.52 mg/L.
- Lei, Peng,Xu, Yan,Du, Juan,Yang, Xin-Ling,Yuan, Hui-Zhu,Xu, Gao-Fei,Ling, Yun
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p. 2544 - 2546
(2016/07/07)
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- Cu(II)-promoted oxidative C-N bond cleavage of N-benzoylamino acids to primary aryl amides
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A novel protocol for CuCl2-promoted oxidative C-N bond cleavage of N-benzoyl amino acids was developed. It is the first example of using accessible amino acid as an ammonia synthetic equivalent for the synthesis of primary aryl amides via CuCl2-promoted oxidative C-N bond cleavage reaction. The present protocol shows excellent functional group tolerance and provides an alternative method for the synthetic of primary aryl amides in 84-96percent yields.
- Chen, Junmin,Liu, Wei,Zhao, Yongli,Zhou, Liandi
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- Palladium(II) complexes with a phosphino-oxime ligand: Synthesis, structure and applications to the catalytic rearrangement and dehydration of aldoximes
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The treatment of [PdCl2(COD)] (COD = 1,5-cyclooctadiene) with 1 and 2 equivalents of 2-(diphenylphosphino)benzaldehyde oxime in dichloromethane at room temperature led to the selective formation of [PdCl2{κ2-(P,N)-2-Ph2PC6H4CHNOH}] (1) and [Pd{κ2-(P,N)-2-Ph2PC6H4CHNOH}2][Cl]2 (2), respectively, which represent the first examples of Pd(II) complexes containing a phosphino-oxime ligand. These compounds, whose structures were fully confirmed by X-ray diffraction methods, were active in the catalytic rearrangement of aldoximes. In particular, using 5 mol% complex 1, a large variety of aldoximes could be cleanly converted into the corresponding primary amides at 100 °C, employing water as solvent and without the assistance of any cocatalyst. Palladium nanoparticles are the active species in the rearrangement process. In addition, when the same reactions were performed employing acetonitrile as solvent, selective dehydration of the aldoximes to form the respective nitriles was observed. For comparative purposes, the catalytic behaviour of an oxime-derived palladacyclic complex has also been briefly evaluated.
- Menéndez-Rodríguez, Lucía,Tomás-Mendivil, Eder,Francos, Javier,Nájera, Carmen,Crochet, Pascale,Cadierno, Victorio
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p. 3754 - 3761
(2015/07/01)
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