- Gram-Scale Preparation of Acyl Fluorides and Their Reactions with Hindered Nucleophiles
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A series of acyl fluorides was synthesized at 100 mmol scale using phase-transfer-catalyzed halogen exchange between acyl chlorides and aqueous bifluoride solution. The convenient procedure consists of vigorous stirring of the biphasic mixture at room temperature, followed by extraction and distillation. Isolated acyl fluorides (usually 7-20 g) display excellent purity and can be transformed into sterically hindered amides and esters when treated with lithium amide bases and alkoxides under mild conditions.
- Barbasiewicz, Micha?,Tryniszewski, Micha?
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- Method for preparing primary and secondary amide compounds
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The invention belongs to the field of organic chemical synthesis, and particularly relates to a method for preparing primary and secondary amide compounds. The method for preparing primary and secondary amide compounds comprises the following steps of carrying out catalytic reduction on an N-substituted amide compound at 30-130 DEG C by using a protic solvent as a reduction reagent and a dichloro(p-methyl isopropylbenzene) ruthenium (II) dimer complex as a catalyst to obtain a reaction solution after the reduction reaction is finished, and carrying out post-treatment on the reaction solution to obtain the corresponding primary amide compound or secondary amide compound. According to the method for preparing the primary and secondary amide compounds, the transfer hydrogenation reaction of nitrogen-oxygen and nitrogen-carbon bonds is realized, the reaction conditions are mild and simple, the substrate application range is wide, the operation is convenient, and the corresponding primary amide compound or secondary amide compound is obtained with high efficiency and high selectivity.
- -
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Paragraph 0046-0056
(2021/02/06)
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- Green and efficient Beckmann rearrangement by Cu(II) contained nano-silica triazine based dendrimer in water
-
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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- 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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- 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.
- -
-
Paragraph 0327-0329
(2021/03/31)
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- Fe3O4@GlcA@Cu-MOF: A Magnetic Metal-Organic Framework as a Recoverable Catalyst for the Hydration of Nitriles and Reduction of Isothiocyanates, Isocyanates, and Isocyanides
-
A novel magnetic metal-organic framework (Fe3O4@GlcA@Cu-MOF) has been prepared and characterized by spectroscopic, microscopic, and magnetic techniques. This magnetically separable catalyst exhibited high catalytic activity for nitrile hydration and the ability to reduce isothiocyanates, isocyanates, and isocyanides with excellent activity and selectivity without any additional reducing agent.
- Ghorbani-Choghamarani, Arash,Taherinia, Zahra
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supporting information
p. 902 - 909
(2020/11/30)
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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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- 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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- 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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- Preparation method of aromatic amide compound
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The present invention provides a preparation method of an aromatic amide compound. In an organic solvent, under the effect of a catalyst, an aromatic acid compound and an amine source are subjected toa dehydration reaction to obtain the aromatic amide compound, wherein the aromatic acid compound is an aromatic acid, a substituted aromatic acid, a heterocyclic aromatic acid or a substituted heterocyclic aromatic acid; and the substituent group of amide is any substituent group of H, a C1-C8 straight-chain alkyl or branched-chain alkyl group, a benzene ring or an aromatic ring. The aromatic amide compound is an important chemical intermediate, and the synthesis method is mild in reaction condition and high in yield.
- -
-
Paragraph 0042-0043
(2020/07/15)
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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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- 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.
- -
-
Paragraph 0018; 0076
(2019/03/28)
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- Method for preparing acidamide from terminal olefin
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The invention belongs to the technical field of preparation of a fine chemical engineering product and synthesis of a medicine intermediate, and particularly relates to a method for preparing acidamide from terminal olefin. According to the method, the terminal olefin is used as a raw material; firstly, dibromohydantoin is added; stirring is performed; then, iodine and ammonium hydroxide or organic amine is added to obtain the corresponding acidamide. The method provided by the invention can be used for converting aromatic ring substituted terminal olefin; the method is also very effective onthe conversion of aliphatic terminal olefin into the acidamide. Compared with the prior art, the method has the advantages that the raw materials are cheap and can be easily obtained; the cost is low;the conditions are mild; the operation is easy; the toxicity of the used reagents is small; good substrate compatibility is realized; great cost and environmental-friendly advantages and wide application prospects are realized.
- -
-
Paragraph 0011; 0012; 0015
(2019/04/04)
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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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- [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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- Base promoted peroxide systems for the efficient synthesis of nitroarenes and benzamides
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A useful and efficient approach for the synthesis of nitroarenes from several aromatic amines (including heterocycles) using peroxide and base has been developed. This oxidative reaction is very easy to handle and afforded the products in good yields. Formation of benzamides from benzylamine was also successfully carried out with this metal-free catalytic system in good to excellent yields.
- Gupta, Sampa,Ansari, Alisha,Sashidhara, Koneni V.
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supporting information
(2019/09/07)
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- Aerobic Activation of C-H Bond in Amines Over a Nanorod Manganese Oxide Catalyst
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The development of heterogeneous catalysts for the synthesis of pharmaceutically relevant compounds is always important for chemistry research. Here, we report a selective aerobic oxidation of aromatic and aliphatic amines to corresponding amides over a nanorod manganese oxide (NR-MnOx) catalyst. The kinetic studies reveal that the NR-MnOx catalyzed amine-to-amide reaction proceeds the oxidative dehydrogenation of the amines into nitriles, followed by hydrolysis of nitrile into amides. The NR?MnOx exhibits fast kinetics and high selectivities in these steps, as well as hinders the by-product formation. More importantly, the NR-MnOx catalyst is stable and reusable in the continuous recycle tests with water as a sole by-product, exhibiting superior sustainability and significant advancement to outperform the traditional amide production route in acidic or basic media with toxic by-products.
- Wang, Hai,Wang, Liang,Wang, Sai,Dong, Xue,Zhang, Jian,Xiao, Feng-Shou
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p. 401 - 406
(2018/08/11)
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- Ionic liquid catalysed aerobic oxidative amidation and thioamidation of benzylic amines under neat conditions
-
Tetrabutylammonium hydroxide (TBAOH) was discovered as a highly efficient and green catalyst for aerobic oxidation of the α-methylene carbon of primary amines as well as benzylic groups into the corresponding amides and ketones under neat conditions. We described herein, ionic liquid TBAOH catalysed aerobic oxidation of benzyl amines to benzamides and with elemental sulfur; the corresponding benzylbenzothioamides were obtained under metal-free, oxidant-free and base-free conditions. Applicability at the gram scale for the synthesis of the desired amides/ketones is also demonstrated with the present protocol.
- Joshi, Abhisek,Kumar, Rahul,Semwal, Rashmi,Rawat, Deepa,Adimurthy, Subbarayappa
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supporting information
p. 962 - 967
(2019/03/11)
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- Chemoselective Synthesis of Aryl Ketones from Amides and Grignard Reagents via C(O)-N Bond Cleavage under Catalyst-Free Conditions
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Conversion of a wide range of N-Boc amides to aryl ketones was achieved with Grignard reagents via chemoselective C(O)-N bond cleavage. The reactions proceeded under catalyst-free conditions with different aryl, alkyl, and alkynyl Grignard reagents. α-Ketoamide was successfully converted to aryl diketones, while α,β-unsaturated amide underwent 1,4-addition followed by C(O)-N bond cleavage to provide diaryl propiophenones. N-Boc amides displayed higher reactivity than Weinreb amides with Grignard reagents. A broad substrate scope, excellent yields, and quick conversion are important features of this methodology.
- Sureshbabu, Popuri,Azeez, Sadaf,Muniyappan, Nalluchamy,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
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p. 11823 - 11838
(2019/10/02)
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- Method for directly synthesizing M-chlorobenzonitrile from M-chlorobenzoic acid and urea
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The invention provides a method for directly synthesizing m-chlorobenzonitrile from m-chlorobenzoic acid and urea, belonging to the technical field of organic chemistry and the technical field of organic fine chemicals. The method for synthesizing m-chlorobenzonitrile comprises the following steps: reacting m-chlorobenzoic acid with urea to generate an intermediate reaction mixture containing m-chlorobenzamide, and carrying out dehydration reaction on the intermediate reaction mixture containing m-chlorobenzamide to generate a mixture containing m-chlorobenzonitrile; and subjecting the mixturecontaining m-chlorobenzonitrile to underpressure distillation to obtain crude nitrile, and subjecting the crude nitrile to washing with water, filtering, drying, and underpressure distillation successively to obtain the finished m-chlorobenzonitrile. The synthetic method of the invention is short in route, simple to operate, easily controllable in reaction conditions, low in production cost and small in environmental pollution; and the synthesized m-chlorobenzonitrile is stable in quality. The intermediate reaction mixture containing m-chlorobenzamide is subjected to ultrasonic or microwave catalytic dehydration, so the yield and the purity of m-chlorobenzonitrile can be remarkably improved.
- -
-
Paragraph 0017; 0020; 0022; 0025
(2019/11/29)
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- Transfer hydrogenation and hydration of aromatic aldehydes and nitriles using heterogeneous NiO nanofibers as a catalyst
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A simple and efficient hydrogen transfer reaction of aldehydes and hydration of nitriles using nickel oxide nanofibers (NiO NFs) as a heterogeneous catalyst is reported. NiO NFs prepared by electrospinning technique was cubic (confirmed by XRD) with an average diameter of 80 nm (obtained from HR-TEM) and utilized as a nanocatalyst for heterogeneous transfer hydrogenation of aromatic aldehydes and hydration of aromatic nitriles. All the reaction products produced with minimum reaction time and maximum yield were confirmed using GC-MS with NIST library. Furthermore, heterogeneity of the catalyst was confirmed with ICP-MS analysis. The as-prepared catalyst was reused for six cycles and was found to be efficient. Hence, the present catalytic synthesis of alcohols and amides may be an economically viable process.
- Thenmozhi,Kadirvelu
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p. 15572 - 15577
(2018/10/04)
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- Direct Transformation of Arylamines to Aryl Halides via Sodium Nitrite and N-Halosuccinimide
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A one-pot universal approach for transforming arylamines to aryl halides via reaction with sodium nitrite (NaNO2) and N-halosuccinimide (NXS) in DMF at room temperature under metal- and acid-free condition is described. This new protocol that is complementary to the Sandmeyer reaction, is suggested to involve the in situ generation of nitryl halide induce nitrosylation of aryl amine to form the diazo intermediate which is halogenated to furnish the aryl halide.
- Mukhopadhyay, Sushobhan,Batra, Sanjay
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supporting information
p. 14622 - 14626
(2018/09/21)
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- Tandem synthesis of aromatic amides from styrenes in water
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An expedient one-pot synthesis of aromatic amides has been reported from styrenes in the presence of N-bromosuccinimide and iodine by using aqueous ammonia in water. The reaction proceeds through the formation of α-bromoketone as an intermediate in the pr
- Sathe, Pratima A.,Karpe, Aniket S.,Parab, Aniket A.,Parade, Babasao S.,Vadagaonkar, Kamlesh S.,Chaskar, Atul C.
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supporting information
p. 2820 - 2823
(2018/06/25)
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- Highly Selective Ruthenium-Catalyzed Direct Oxygenation of Amines to Amides
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Reports on aerobic oxidation of amines to amides are rare, and those reported suffer from several limitations like poor yield or selectivity and make use of pure oxygen under elevated pressure. Herein, we report a practical and an efficient ruthenium-catalyzed synthetic protocol that enables selective oxidation of a broad range of primary aliphatic, heterocyclic and benzylic amines to their corresponding amides, using readily available reagents and ambient air as the sole oxidant. Secondary amines instead, yield benzamides selectively as the sole product. Mechanistic investigations reveal intermediacy of nitriles, which undergo hydration to afford amide as the final product.
- Ray, Ritwika,Hazari, Arijit Singha,Chandra, Shubhadeep,Maiti, Debabrata,Lahiri, Goutam Kumar
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supporting information
p. 1067 - 1071
(2018/01/03)
-
- 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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- 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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- 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)
-
- 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
-
supporting information
p. 7222 - 7225
(2018/01/02)
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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
-
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
-
supporting information
p. 2512 - 2516
(2017/05/31)
-
- A mild hydration of nitriles catalysed by copper(ii) acetate
-
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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- Chlorophosphines as auxiliary ligands in ruthenium-catalyzed nitrile hydration reactions: Application to the preparation of β-ketoamides
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The catalytic hydration of nitriles into amides, in water under neutral conditions, has been studied using a series of arene-ruthenium(ii) complexes containing commercially available chlorophosphines as auxiliary ligands, i.e. compounds [RuCl2(η6-p-cymene)(PR2Cl)] (R = aryl, heteroaryl or alkyl group). In the reaction medium, the coordinated chlorophosphines readily undergo hydrolysis to generate the corresponding phosphinous acids PR2OH, which are well-known "cooperative" ligands for this catalytic transformation. Among the complexes employed, best results were obtained with [RuCl2(η6-p-cymene){P(4-C6H4F)2Cl}]. Performing the catalytic reactions at 40 °C with 2 mol% of this complex, a large variety of organonitriles could be selectively converted into the corresponding primary amides in high yields and relatively short times. The application of [RuCl2(η6-p-cymene){P(4-C6H4F)2Cl}] in the preparation of synthetically useful β-ketoamides is also presented.
- González-Fernández, Rebeca,González-Liste, Pedro J.,Borge, Javier,Crochet, Pascale,Cadierno, Victorio
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p. 4398 - 4409
(2016/07/06)
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- Supported Gold Nanoparticles-Catalyzed Microwave-Assisted Hydration of Nitriles to Amides under Base-Free Conditions
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Polystyrene-supported gold (Au@PS) nanoparticles were synthesized by the reduction deposition approach and well characterized by UV-visible, XRD, TEM, SAED, EDX, and XPS studies. The Au@PS was applied as catalyst for the hydration of nitriles to amides in water under microwave irradiation. Several functionalized aromatic, heterocyclic and aliphatic nitriles were found to be active for synthesis of the corresponding amides where no activation of water by base, ligand and support is needed. Easy recovery, negligible leaching and recyclability for up to eight runs are added advantages of the catalyst under water-mediated reaction conditions. (Figure presented.).
- Kumar, Sandeep,Sharma, Saurabh,Das, Pralay
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supporting information
p. 2889 - 2894
(2016/09/16)
-
- Clean synthesis of primary to tertiary carboxamides by CsOH-catalyzed aminolysis of nitriles in water
-
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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- Bis(allyl)-ruthenium(IV) complexes with phosphinous acid ligands as catalysts for nitrile hydration reactions
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Several mononuclear ruthenium(iv) complexes with phosphinous acid ligands [RuCl2(η3:η3-C10H16)(PR2OH)] have been synthesized (78-86% yield) by treatment of the dimeric precursor [{RuCl(μ-Cl)(η3:η3-C10H16)}2] (C10H16 = 2,7-dimethylocta-2,6-diene-1,8-diyl) with 2 equivalents of different aromatic, heteroaromatic and aliphatic secondary phosphine oxides R2P(O)H. The compounds [RuCl2(η3:η3-C10H16)(PR2OH)] could also be prepared, in similar yields, by hydrolysis of the P-Cl bond in the corresponding chlorophosphine-Ru(iv) derivatives [RuCl2(η3:η3-C10H16)(PR2Cl)]. In addition to NMR and IR data, the X-ray crystal structures of representative examples are discussed. Moreover, the catalytic behaviour of complexes [RuCl2(η3:η3-C10H16)(PR2OH)] has been investigated for the selective hydration of organonitriles in water. The best results were achieved with the complex [RuCl2(η3:η3-C10H16)(PMe2OH)], which proved to be active under mild conditions (60 °C), with low metal loadings (1 mol%), and showing good functional group tolerance.
- Tomás-Mendivil, Eder,Francos, Javier,González-Fernández, Rebeca,González-Liste, Pedro J.,Borge, Javier,Cadierno, Victorio
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p. 13590 - 13603
(2016/09/04)
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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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supporting information
p. 2544 - 2546
(2016/07/07)
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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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- 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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- Exfoliation effect of PEG-type surfactant on Pd supported GO (SE-Pd(nanoparticle)/GO) in cascade synthesis of amides: A comparison with Pd(nanoparticle)/rGO
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In the presence investigation, a cascade method for the synthesis of primary amides is discussed by the catalysis of Pd supported onto graphene oxide (Pd/GO) nanosheets. Also, the effect of different polyethyleneglycol-type (PEG-type) polyethers including PEG-300, P123 and F127 on the catalytic activity of Pd/rGO is studied in the the reaction of aldehyde and hydroxylamine hydrochloride to give benzamide. Addition of PEG-type polyethers played an important role in raising the catalytic power of Pd(nanoparticle)/GO by exfoliation of GO sheets. The present paper introduces Pd(nanoparticle)/GO as first Pd supported GO for the synthesis of primary amides through this method. This catalyst was highly active, efficient, tolerant, and environmentally benign in one-pot conditions with recyclability at least for 8 runs. Also, this study suggests the prevailing catalytic activity of Pd(nanoparticle)/GO rather to Pd(nanoparticle)/rGO in a comparitive experiment.
- Rostamnia, Sadegh,Doustkhah, Esmail,Zeynizadeh, Behzad
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- Copper nanoparticles on charcoal: An effective nanocatalyst for the synthesis of enol carbamates and amides via an oxidative coupling route
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The catalytic activity of copper nanoparticles on charcoal (Cu/C) was investigated as an environmentally friendly heterogeneous catalyst for the synthesis of enol carbamates and amides via the oxidative coupling of N,N-dialkyl formamides with 1,3-dicarbonyl compounds and aromatic aldehydes with amine hydrochloride salts, respectively. Various enol carbamates and amides were synthesized in moderate to good yields using this method. Moreover, the catalyst could be recovered and subsequently reused in further reactions.
- Saberi, Dariush,Mansoori, Sakineh,Ghaderi, Esmali,Niknam, Khodabakhsh
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supporting information
p. 95 - 99
(2015/12/23)
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- Direct oxidative esterification of alcohols and hydration of nitriles catalyzed by a reusable silver nanoparticle grafted onto mesoporous polymelamine formaldehyde (AgNPs@mPMF)
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A nitrogen-rich mesoporous organic polymer was synthesized as a novel support. A silver nanoparticle was synthesized and grafted onto it. The prepared catalyst (AgNPs@mPMF) was characterized by powder X-ray diffraction (XRD), scanning electron microscopy(SEM) and energy dispersive X-ray spectrometry (EDS), thermogravimetric analysis (TGA), high-resolution transmission electron microscopy (HRTEM), UV-vis diffuse reflectance spectroscopy (DRS), N2 adsorption, Raman spectroscopy and EPR study. The catalytic activity was evaluated for the oxidative esterification reaction of alcohols and hydration of nitriles. The oxidative esterification reaction was carried out for various activated alcohols giving excellent yields of the corresponding ester products. The catalyst was also efficient in the hydration of nitriles. Both reactions were optimized by varying the bases, temperatures and solvents. The catalyst can be facilely recovered and reused six times without a significant decrease in its activity and selectivity.
- Ghosh, Kajari,Iqubal, Md. Asif,Molla, Rostam Ali,Mishra, Ashutosh,Kamaluddin,Islam, Sk Manirul
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p. 1606 - 1622
(2015/04/27)
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- Transition-metal-free hydration of nitriles using potassium tert -butoxide under anhydrous conditions
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Potassium tert-butoxide acts as a nucleophilic oxygen source during the hydration of nitriles to give the corresponding amides under anhydrous conditions. The reaction proceeds smoothly for a broad range of substrates under mild conditions, providing an efficient and economically affordable synthetic route to the amides in excellent yields. This protocol does not need any transition-metal catalyst or any special experimental setup and is easily scalable to bulk scale synthesis. A single-electron-transfer radical mechanism as well as an ionic mechanism have been proposed for the hydration process.
- Midya, Ganesh Chandra,Kapat, Ajoy,Maiti, Subhadip,Dash, Jyotirmayee
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supporting information
p. 4148 - 4151
(2015/05/05)
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- Hydration of nitriles to amides by a chitin-supported ruthenium catalyst
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Chitin-supported ruthenium (Ru/chitin) promotes the hydration of nitriles to carboxamides under aqueous conditions. The nitrile hydration can be performed on a gram-scale and is compatible with the presence of various functional groups including olefins, aldehydes, carboxylic esters and nitro and benzyloxycarbonyl groups. The Ru/chitin catalyst is easily prepared from commercially available chitin, ruthenium(III) chloride and sodium borohydride. Analysis of Ru/chitin by high-resolution transmission electron microscopy indicates the presence of ruthenium nanoparticles on the chitin support.
- Matsuoka, Aki,Isogawa, Takahiro,Morioka, Yuna,Knappett, Benjamin R.,Wheatley, Andrew E. H.,Saito, Susumu,Naka, Hiroshi
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p. 12152 - 12160
(2015/02/19)
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- An aerobic oxidative synthesis of aryl nitriles and primary aryl amides from benzylic alcohols catalyzed by a polymer supported Cu(II) complex
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A new polymer supported Cu(II) complex has been synthesized and characterized. The catalytic performance of the complex has been tested for the direct conversion of benzylic alcohols to aryl nitriles. In this reaction ammonium formate was used as the nitrogen source and O2 as the oxidant. Furthermore, the copper-catalyzed one-pot synthesis of primary aryl amides from alcohols was also achieved. The effects of solvents, reaction time and catalyst amount for the aryl nitriles and aryl amides synthesis were reported. This catalyst showed excellent catalytic activity and recyclability. The polymer supported Cu(II) catalyst could be easily recovered by filtration and reused more than five times without appreciable loss of its initial activity.
- Molla, Rostam Ali,Ghosh, Kajari,Tuhina,Manirul Islam
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p. 921 - 930
(2015/02/19)
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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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- Polymer-anchored Ru(II) complex as an efficient catalyst for the synthesis of primary amides from nitriles and of secondary amides from alcohols and amines
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A polymer-anchored ruthenium(II) catalyst was synthesized and characterized. Its catalytic activity was evaluated for the preparation of primary amides from aqueous hydration of nitriles in neutral condition. A range of nitriles were successfully converted to their corresponding amides in good to excellent yields. The catalyst was also effective in the preparation of secondary amides from the coupling of alcohols and amines. The catalyst can be facilely recovered and reused six times without a significant decrease in its activity.
- Islam, Sk Manirul,Ghosh, Kajari,Roy, Anupam Singha,Molla, Rostam Ali
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p. 900 - 907
(2015/02/19)
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- Investigation of binap-based hydroxyphosphine arene-ruthenium(II) complexes as catalysts for nitrile hydration
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The binap-based hydroxyphosphine-(η6-arene)-ruthenium(ii) complexes [RuX{η6:κ1(P)-PPh2-binaphthyl}{PPh2(OH)}][OTf] (X = OTf (4), Cl (5)) have been evaluated as potential catalysts for the selective hydration of nitriles to primary amides. The triflate derivative 4 proved to be the most active, being able to hydrate a large variety of aromatic, heteroaromatic, α,β-unsaturated and aliphatic nitriles in pure water at 100°C. The utility of complex 4 to promote the catalytic rearrangement of aldoximes has also been demonstrated. In addition, insights about the role played by the hydroxyphosphine ligand PPh2(OH) during the catalytic reactions are given.
- Toms-Mendivil, Eder,Menndez-Rodrguez, Luca,Francos, Javier,Crochet, Pascale,Cadierno, Victorio
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p. 63466 - 63474
(2015/02/19)
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- Efficient and selective nitrile hydration reactions in water catalyzed by an unexpected dimethylsulfinyl anion generated in situ from CsOH and DMSO
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Unexpected dimethylsulfinyl anions (I), generated in situ from the superbase system CsOH-DMSO, was found to be a highly active catalyst for controllable nitrile hydration reactions in water, which selectively afforded the versatile amides via interesting Cs-activated I-catalyzed direct and indirect hydration mechanisms involving an O-transfer process from DMSO onto the nitriles. the Partner Organisations 2014.
- Chen, Haonan,Dai, Wujie,Chen, Yi,Xu, Qing,Chen, Jianhui,Yu, Lei,Zhao, Yajuan,Ye, Mingde,Pan, Yuanjiang
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supporting information
p. 2136 - 2141
(2014/04/17)
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- An efficient ruthenium(iv) catalyst for the selective hydration of nitriles to amides in water under mild conditions
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A Ru(iv) catalyst able to promote the selective hydration of nitriles to amides in water, at low metal loadings and under mild conditions, is presented. This journal is the Partner Organisations 2014.
- Tomás-Mendivil, Eder,Suárez, Francisco J.,Díez, Josefina,Cadierno, Victorio
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supporting information
p. 9661 - 9664
(2014/08/18)
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