- Hollow fiber liquid-phase microextraction with in situ derivatization combined with gas chromatography-mass spectrometry for the determination of root exudate phenylamine compounds in hot pepper (Capsicum annuum L.)
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Hollow fiber liquid-phase microextraction (HF-LPME) with derivatization was developed for the determination of three root exudate phenylamine compounds in hot pepper (Capsicum annuum L.) by gas chromatography-mass spectrometry (GC-MS). The performance and applicability of the proposed procedure were evaluated through the extraction of 1-naphthylamine (1-NA), diphenylamine (DPA), and N-phenyl-2- naphthaleneamine (N-P-2-NA) in a recirculating hydroponic solution of hot pepper. Parameters affecting the extraction efficiency were investigated. The calibration curves showed a good linearity in the range of 0.1-10 μg mL-1. The limits of detection (S/N = 3) for the three compounds were 0.096, 0.074, and 0.057 μg mL-1, respectively. The enrichment factors reached 174, 196, and 230 at the concentration of 5 μg mL -1, and relative standard deviations (RSD) of 9.5, 8.6, and 7.8% and 8.4, 7.6, and 6.2% were obtained at concentrations of 2 and 5 μg mL -1 for 1-NA, DPA, and N-P-2-NA, respectively. Recoveries ranging from 90.2 to 96.1% and RSDs below 9.1% were obtained when HF-LPME with in situ derivatization was applied to determine root exudate 1-NA, DPA, and N-P-2-NA after 15 and 30 days of culture solution, respectively.
- Sun, Haiyan,Wang, Yan
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Read Online
- Method for preparing aryl amide compound by catalyzing carbonylation of aryl tertiary amine through metal-free catalytic system
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The invention discloses a method for preparing aryl amide compounds by catalyzing aryl tertiary amine carbonylation through a metal-free catalytic system. The method is characterized in that in a reaction solvent, carbonyl molybdenum is used as a substitute carbonyl source, an organic base is used as a main catalyst, and methyl iodide is used as a catalyst promoter; and carbonylation of aryl tertiary amine is catalyzed under normal pressure to prepare the aryl amide compound. The reaction formula of synthesis is shown in the specification, wherein R is one of CH3, C2H5, pheyl, F, CL, Br or CN. According to the present invention, the organic base is adopted as the main catalyst, the iodomethane is adopted as the catalyst promoter, the carbonyl molybdenum is adopted as the substitute carbonyl source, and the aryl tertiary amine carbonylation can be efficiently catalyzed at the reaction temperature of 140 DEG C to prepare the aryl amide compound, so that the atom economy of the reaction is effectively improved, and a wide application prospect is provided; the molybdenum carbonyl is used as the substitute carbonyl source, so that the potential safety hazard of carbon monoxide is avoided; and the reaction can be carried out under normal pressure in the reaction process, and high-pressure reaction equipment is not needed.
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Paragraph 0028-0043; 0050-0063; 0066-0067
(2021/08/19)
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- Preparation and catalytic evaluation of a palladium catalyst deposited over modified clinoptilolite (Pd&at;MCP) for chemoselective N-formylation and N-acylation of amines
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Novel palladium nanoparticles stabilized by clinoptilolite as a natural inexpensive zeolite prepared and used for N-formylation and N-acylation of amines at room temperature at environmentally benign reaction conditions in good to excellent yields. Pd (II) was immobilized on the surface of clinoptilolite via facile multi-step amine functionalization to obtain a sustainable, recoverable, and highly active nano-catalyst. The structural and morphological characterizations of the catalyst carried out using XRD, FT-IR, BET and TEM techniques. Moreover, the catalyst is easily recovered using simple filtration and reused for 7 consecutive runs without any loss in activity.
- Amirsoleimani, Mina,Khalilzadeh, Mohammad A.,Zareyee, Daryoush
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- Nickel/Photoredox-Catalyzed Methylation of (Hetero)aryl Chlorides Using Trimethyl Orthoformate as a Methyl Radical Source
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Methylation of organohalides represents a valuable transformation, but typically requires harsh reaction conditions or reagents. We report a radical approach for the methylation of (hetero)aryl chlorides using nickel/photoredox catalysis wherein trimethyl orthoformate, a common laboratory solvent, serves as a methyl source. This method permits methylation of (hetero)aryl chlorides and acyl chlorides at an early and late stage with broad functional group compatibility. Mechanistic investigations indicate that trimethyl orthoformate serves as a source of methyl radical via β-scission from a tertiary radical generated upon chlorine-mediated hydrogen atom transfer.
- Kariofillis, Stavros K.,Shields, Benjamin J.,Tekle-Smith, Makeda A.,Zacuto, Michael J.,Doyle, Abigail G.
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supporting information
p. 7683 - 7689
(2020/04/22)
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- Direct Synthesis of N,N-Disubstituted Formamides by Oxidation of Imines Using an HFIP/UHP System
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The straightforward synthesis of N,N-disubstituted formamides using a combination of 1,1,1,3,3,3-hexafluoroispropanol (HFIP) and H2O2 is described. The unique features of HFIP allowed the utilization of a green oxidant such as H2O2, and the products, arising from an oxidation-rearrangement sequence, were obtained in good to high yields under smooth reaction conditions.
- Llopis, Natalia,Gisbert, Patricia,Baeza, Alejandro
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p. 11072 - 11079
(2020/10/12)
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- Carbonylation of C?N Bonds in Tertiary Amines Catalyzed by Low-Valent Iron Catalysts
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The first iron catalysts able to promote the formal insertion of CO into the C?N bond of amines are reported. Using low-valent iron complexes, including K2[Fe(CO)4], amides are formed from aromatic and aliphatic amines, in the presence of an iodoalkane promoter. Inorganic Lewis acids, such as AlCl3 and Nd(OTf)3, have a positive influence on the catalytic activity of the iron salts, enabling the carbonylation at a low pressure of CO (6 to 8 bars).
- Nasr Allah, Tawfiq,Savourey, Solène,Berthet, Jean-Claude,Nicolas, Emmanuel,Cantat, Thibault
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supporting information
p. 10884 - 10887
(2019/07/15)
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- Amide Synthesis from Thiocarboxylic Acids and Amines by Spontaneous Reaction and Electrosynthesis
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Amide bond formation is one of the most important basic reactions in chemistry. A catalyst-free approach for constructing amide bonds from thiocarboxylic acids and amines was developed. The mechanistic studies showed that the disulfide was the key intermediate for this amide synthesis. Thiobenzoic acids could be automatically oxidized to disulfides in air, thioaliphatic acids could be electro-oxidized to disulfides, and the resulting disulfides reacted with amines to give the corresponding amides. By this method, various amides could be easily synthesized in excellent yields without using any catalyst or activator. The successful synthesis of bioactive compounds also highlights the synthetic utility of this strategy in medicinal chemistry.
- Tang, Li,Matuska, Jack H.,Huang, Yu-Han,He, Yan-Hong,Guan, Zhi
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p. 2570 - 2575
(2019/06/13)
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- Method for preparing N,N-diarylamide derivatives
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The invention provides a method for preparing N,N-diarylamide derivatives and belongs to the technical field of chemical synthesis. The method comprises the following steps: taking N-arylamide and phenylboronic acid as raw materials, stirring in an organic solvent under blue light irradiation for 30-44 hours so as to obtain crude N,N-diarylamide, extracting and washing the crude product, and performing column chromatography isolation, thereby obtaining the high-purity N,N-diarylamide derivative. The method disclosed by the invention is simple and readily available in raw materials, mild in reaction condition and simple in operation, and the N,N-diarylamide derivatives with structural diversity can be easily obtained by changing the structures of the raw materials and have excellent application and market value.
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Paragraph 0024-0026; 0063
(2019/02/04)
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- Biogenic CuFe2O4 magnetic nanoparticles as a green, reusable and excellent nanocatalyst for acetylation reactions under solvent-free conditions
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A convenient green method has been developed for the synthesis of biogenic CuFe2O4 magnetic nanoparticles using tea extracts within a very short reaction time. The prepared nanoparticles with an average size of 8.78 nm have been used as an effective catalyst for the acetylation of various alcohols, phenols and amines in good to excellent yields under solvent-free conditions. The catalyst was characterized by XRD, XPS, VSM, SEM and TEM study. A magnetic study of the fresh and recycled catalyst after the fourth cycle was performed by VSM measurement. The main advantages of this protocol are simple biogenic synthesis of the catalyst, a reusable and heterogeneous catalytic system, and short reaction times with excellent yields.
- Chutia, Rituparna,Chetia, Bolin
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p. 15200 - 15206
(2018/09/29)
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- Synthesis of a Zeolitic Imidazolate-Zinc Metal-Organic Framework and the Combination of its Catalytic Properties with 2,2,2-Trifluoroethanol for N-Formylation
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A novel protocol is reported for the N-formylation of amines with formic acid by using the nanoporous zeolitic imidazolate framework ZIF-8 as a heterogeneous catalyst in 2,2,2-trifluoroethanol.
- Alamgholiloo, Hassan,Rostamnia, Sadegh,Hassankhani, Asadollah,Banaei, Reza
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supporting information
p. 1593 - 1596
(2018/06/08)
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- Method for preparing N-aryl tertiary amide with substituted Meldrum's acid as acylating agent in water phase
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The invention discloses a method for preparing N-aryl tertiary in a water phase. According to the method, water is used as the solvent, and substituted Meldrum's acid and N-aryl secondary amine react at 80-100 DEG C for 1-10 h to obtain the N-aryl tertiary. The molar ratio of substituted Meldrum's acid to N-aryl secondary amine is 1:10-10:1. The reaction concentration of substituted Meldrum's acid or N-aryl secondary amine is 0.5-4 mol/L. The method overcomes the defect that in the prior art, acyl chloride, anhydride, dehydration coupling reagent, organic solvent, phase transfer catalyst or metal catalyst needs to be adopted, and has the advantages that by using substituted Meldrum's acid as an acylating agent, pre-activating of carboxylic acid or using of a dehydration coupling reagent is avoided; due to the fact that substituted Meldrum's acid is easy to prepare, using of certain carboxylic acid and activated derivatives which are hard to get or expensive is avoided; water is used as the solvent, so that using of toxic organic solvent is avoided; no acid, alkali or metal catalyst is adopted, so that influences of acid and alkali on sensitive groups and equipment and metal ion residues in products are avoided. The synthesis method can play an important role in industrial production of N-aryl tertiary, especially N-aryl tertiary of complex carboxylic acid.
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Paragraph 0014; 0035
(2017/04/22)
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- Interception of amide ylides with sulfonamides: Synthesis of (: E)- N -sulfonyl amidines catalyzed by Zn(OTf)2
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Through the interception of amide ylides with sulfonamides, we herein report the first general example of an intermolecular condensation reaction between sulfonamides and amides. Beyond formamides, this approach was successfully applied to a variety of lactams and linear amides, giving rise to a broad array of (E)-N-sulfonyl amidines.
- Chen, Jijun,Long, Wenhao,Fang, Shangwen,Yang, Yonggang,Wan, Xiaobing
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supporting information
p. 13256 - 13259
(2017/12/26)
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- SBA-15 Immobilized Phenanthroline-Copper(I) Complex as a Recyclable Efficient Catalyst for N-Arylation of Amides and N-H Heterocycles with Aryl Halides
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5-(N,N-bis-3-(triethoxysilyl) propyl) ureyl-1,10-phenanthroline was prepared and successively grafted onto mesoporous silica of SBA-15 to get SBA-15 anchored ligand which was then reacted with Cu(I) to get SBA-15 anchored complex as the heterogeneous copper catalyst. This catalyst was characterized by FT-IR, XRD, CHN, AAS, TGA, EDAX, BET, SEM and TEM. The activities of the catalyst were tested in C-N cross-coupling of amides and N-H heterocycle compounds with aryl halides. The catalyst showed high catalytic activities for these cross-coupling reactions providing good to excellent yields of desired products. Moreover, the catalyst can be easily recovered by simple filtration and reused several times without significant loss of its catalytic activity.
- Hosseinzadeh, Rahman,Aghili, Nora,Tajbakhsh, Mahmood
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p. 193 - 203
(2016/03/12)
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- Highly efficient and recyclable acetylation of phenols and alcohols by nickel zirconium phosphate under solvent-free conditions
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Nickel zirconium phosphate nanoparticles have been used as an efficient catalyst for the acetylation of a wide range of alcohols and phenols with acetic anhydride in good to excellent yields under solvent-free conditions. The steric and electronic properties of the different substrates had a significant influence on the reaction conditions required to achieve the acetylation. The catalyst used in the current study was characterized by inductively coupled plasma optical emission spectroscopy, X-ray diffraction, N2 adsorption-desorption, scanning electron microscopy, and transmission electron microscopy. This nanocatalyst could also be recovered and reused at least six times without any discernible decrease in its catalytic activity.
- Hajipour, Abdol Reza,Karimi, Hirbod,Kohi, Afshin
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- Efficient tandem aqueous room temperature oxidative amidations catalysed by supported Pd nanoparticles on graphene oxide
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Pd nanoparticles deposited onto graphene oxide nanosheets (SE-GO/PdNPs) were found to successfully promote two oxidative processes for the synthesis of amides, providing alternative possibilities to these important compounds. SE-GO/PdNPs exhibited excellent activities with an optimum efficiency in tandem one-pot conversion of alcohols to amides in the presence of various amines.
- Rostamnia, Sadegh,Doustkhah, Esmail,Golchin-Hosseini, Habib,Zeynizadeh, Behzad,Xin, Hongchuan,Luque, Rafael
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p. 4124 - 4133
(2016/07/06)
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- Transition metal-free N-arylation of secondary amides through iodonium salts as aryne precursors
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By using a diaryliodonium salt as a benzyne precursor, a transition metal-free approach for N-arylation of secondary amides is developed. This novel benzyne precursor, which can be prepared easily by a one step process from an aryl iodide, shows different reactivities with previous benzyne precursors in the N-arylation reaction. Mechanistic studies confirm the involvement of benzyne species (generated in situ from the diaryliodonium salts) as key intermediates.
- Wang, Ming,Huang, Zhijian
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supporting information
p. 10185 - 10188
(2016/11/11)
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- An eco-friendly and highly efficient route for N-acylation under catalyst-free conditions
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An eco-friendly, simple, mild, chemoselective and highly efficient procedure for the acylation of primary and secondary amine function in various structurally and electronically aliphatic and aromatic compounds affording their corresponding N-Ac derivatives is developed. Mild conditions, simplicity and easier work-up are the main advantages of this method.
- Ouarna, Souad,K'tir, Hacène,Lakrout, Salah,Ghorab, Hamida,Amira, A?cha,Aouf, Zineb,Berredjem, Malika,Aouf, Nour-Eddine
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p. 913 - 919
(2015/10/28)
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- Metal-free n -arylation of secondary amides at room temperature
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The arylation of secondary acyclic amides has been achieved with diaryliodonium salts under mild and metal-free conditions. The methodology has a wide scope, allows synthesis of tertiary amides with highly congested aryl moieties, and avoids the regioselectivity problems observed in reactions with (diacetoxyiodo)benzene.
- Tinnis, Fredrik,Stridfeldt, Elin,Lundberg, Helena,Adolfsson, Hans,Olofsson, Berit
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p. 2688 - 2691
(2015/06/16)
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- An attractive route to transamidation catalysis: Facile synthesis of new o-aryloxide-N-heterocyclic carbene ruthenium(II) complexes containing trans triphenylphosphine donors
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Well-defined robust ruthenium(II) complexes 3a-d bearing o-aryloxide-N-heterocyclic carbene ligands with different wingtip substituents (3a (R = Me), 3b (R = Ph), 3c (R = iPr) and 3d (R = Mes)) in the imidazole ring were synthesized in good yields by the reaction of imidazolium proligands with metal precursor [RuHCl(CO)(PPh3)3] by transmetallation from the corresponding silver carbene complexes. All the Ru(II)-NHC complexes have been characterized by elemental analyses, spectroscopic methods as well as ESI mass spectrometry. The molecular structure of the complex 3a was identified by means of single-crystal X-ray diffraction analysis, which revealed that the complexes possess a distorted octahedral geometry. In order to explore the catalytic potential of the synthesized complexes, all the four [Ru-NHC] complexes [3a-d] were tested as catalysts for transamidation of carboxamides with amines. Notably, the complex 3a was found to be very efficient and versatile catalyst toward transamidation of a wide range of amides with amines.
- Nirmala, Muthukumaran,Prakash, Govindan,Viswanathamurthi, Periasamy,Malecki, Jan Grzegorz
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- Rice husk: Introduction of a green, cheap and reusable catalyst for the protection of alcohols, phenols, amines and thiols
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A mild, efficient and eco-friendly protocol for the chemoselective protection of benzylic and primary and less hindered secondary aliphatic alcohols and phenols as trimethylsilyl ethers and different types of amines as N-tert-butylcarbamates is developed using rice husk (RiH) as the catalyst. This reagent is also able to catalyze the acetylation of alcohols, phenols, thiols and amines with acetic anhydride. Easy work-up, relatively short reaction times, excellent yields and low cost, availability and reusability of the catalyst are the striking features of this methodology, which can be considered to be one of the best and general methods for the protection of alcohols, phenols, thiols and amines. In addition, the use of a green reagent in the above-mentioned reactions results in a reduction of environmental pollution and of the cost of the applied methods.
- Shirini, Farhad,Akbari-Dadamahaleh, Somayeh,Mohammad-Khah, Ali,Aliakbar, Ali-Reza
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p. 164 - 170
(2014/03/21)
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- Rice husk ash: A new, cheap, efficient, and reusable reagent for the protection of alcohols, phenols, amines, and thiols
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Amild, efficient, and eco-friendly protocol for the protection of alcohols and phenols as trimethylsilyl ethers has been developed using rice husk ash as a reagent. This reagent is also able to catalyze the acetylation of alcohols, phenols, thiols, and amines with acetic anhydride. All reactions were performed under mild conditions in good to high yields. Copyright
- Shirini,Akbari-Dadamahaleh, Somayeh,Mohammad-Khah, Ali
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p. 577 - 586
(2014/06/09)
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- Preparation and characterization of multi-walled carbon nanotubes (MWCNTs), functionalized with phosphonic acid (MWCNTs-C-PO3H2) and its application as a novel, efficient, heterogeneous, highly selective and reusable catalyst for acetylation of alcohols, phenols, aromatic amines, and thiols
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A novel, efficient, heterogeneous, and reusable multi-walled carbon nanotubes (MWCNTs), functionalized with phosphonic acid (MWCNTs-C-PO 3H2) has been synthesized. The synthesized CNTs were characterized using some electron microscopic techniques such as scanning electron microscopy (SEM), atomic force microscopy (AFM), Energy dispersive X-ray spectroscopy (EDAX), and also some thermal and spectroscopic methods such as thermogravimetry (TG). The nitrogen adsorption behavior of the MWCNTs-C-PO3H2 catalyst was evaluated using the TG instrumentation system at 25°C. The catalyst was applied successfully for highly efficient and selective acetylation of alcohols, phenols, thiols and aromatic amines with acetic anhydride at room temperature under solvent-free conditions. The reusability of the catalyst was checked and the recovered catalyst was reused for five runs without significant loss in activity.
- Dehghani, Farzaneh,Sardarian, Ali Reza,Doroodmand, Mohammad Mehdi
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p. 673 - 684
(2014/05/20)
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- Ligand-free Ullmann-type C-heteroatom couplings under practical conditions
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A new practical ligand-free protocol for copper-catalyzed C-heteroatom cross-coupling reactions (Ullmann-type) is described. The use of dimethyl sulfoxide (DMSO) as the solvent overcomes the need to use organic auxiliary ligands; thus, DMSO is revealed as a nontoxic and superior solvent for Ullmann-type coupling reactions. This method allows the arylation of a wide range of amides, alcohols, and amines under practical conditions with bromobenzene and iodobenzene derivatives and will likely find direct application in current organic synthesis. The competitive reactivity among different functional groups is reported and rationalized, and the possibility to achieve selective arylation reactions is demonstrated. Copyright
- Gueell, Imma,Ribas, Xavi
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p. 3188 - 3195
(2014/06/09)
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- Selectivities in acylation of primary and secondary amine with diacylaminoquinazolinones and diacylanilines
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The diacylaminoquinazolinones are highly selective acylating agents for primary amines in the presence of secondary amines. The chemoselective N-acetylation reagents have been investigated using 2-substituted N,Ndiacylaminoquinazolinones (DAQs) and 2-substitued-N-diacylanilines (DAAs). Determination of the selectivity ratios have been made by comparison of the crude product in each case with authentic samples of the amide products using NMR spectroscopy. The control experiments in which pairs of amines compete for acetyl chloride show some selectivity but not comparable with that of DAQs and DAAs selectivity. When the DAQs, DAAs and acetyl chloride react with mixtures of pyrrolidine and piperidine, they give amides in the corresponding ratios. The DAQs 1 and 2 react entirely with diethylamine without any competitive reaction with diphenylamine. The high level of chemoselectivity has also been observed when the 1 and 2 react exclusively with the ethanolamine without any competitive reaction with diethanolamine. Moreover, 1 and 2 react with succinimide without any competitive reaction with phthalimide.
- Al-Sehemi, Abdullah G.,Al-Amri, Reem S. Abdul-Aziz,Irfan, Ahmad
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p. 1115 - 1121
(2014/10/15)
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- Malonic ester amide synthesis: An efficient methodology for synthesis of amides
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A general methodology malonic ester amide synthesis has been demonstrated, which uses α-substituted/unsubstituted diethyl malonates for the decarboxylative acylation of various aromatic/heteroaromatic primary/secondary amines to form one-carbon homologated amides, thus providing easy access to amides with odd/even chain lengths and an array of substituents on the alkyl/aryl part while avoiding use of acyl chlorides or peptide coupling reagents. Copyright
- Mahajan, Pankaj S.,Mahajan, Jyoti P.,Mhaske, Santosh B.
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p. 2508 - 2516
(2013/07/25)
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- On the oxidation of different iminic bonds by excess of 3-chloroperbenzoic acid
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In the present work the behavior of different substituted iminic bonds toward the oxidative action of 3-chloroperbenzoic acid is reported. The C=N bond was or was not oxidized to oxaziridines, amides, oximes, nitroso-, nitro-, and azodioxy compounds depending on the substituents at the iminic group and on the imine/MCPBA stoichiometric ratio.
- Troisis, Lutiginon,Carrozzo, Marina M.,Citti, Cinzia,Falcicchio, Aurelia,Mansueto, Rosmara,Rosato, Francesca,Cannazza, Giuseppe
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supporting information
p. 53 - 56
(2013/02/23)
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- An efficient copper-catalyzed N-arylation of amides: Synthesis of N-arylacrylamides and 4-amido-N-phenylbenzamides
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Copper-catalyzed intermolecular C-N bond-forming reactions between aryl iodides and amides are described using sodium ascorbate, which is both cheap and nontoxic, as the additive. A variety of functionalized amides including some practical, unique secondary amides, such as N-arylacrylamides and 4-amido-N-phenylbenzamides, which are difficult to obtain by the classical methods, are prepared. Furthermore, some tertiary amides are prepared by using copper thiophenecarboxylate.
- Quan, Zheng-Jun,Xia, Hai-Dong,Zhang, Zhang,Da, Yu-Xia,Wang, Xi-Cun
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p. 8368 - 8374
(2013/09/02)
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- Synthesis, characterization and properties of copper(I) complexes with bis(diphenylphosphino)-ferrocene ancillary ligand
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Three copper(I) complexes (2-4) containing dppf ancillary ligand (dppf = bis(diphenylphosphino)-ferrocene) were synthesized when chloride-bridged copper(I) complex 1 reacted with acetanilide and characterized by IR, element analysis and NMR spectrum. And the crystal structures of complexes 2 and 4 have been determined by X-ray diffraction method. Complex 2, an acetate-bridged copper(I) complex, was obtained under N2 atmosphere in un-dried solvent; the acetate ion came from the hydrolysis reaction of acetanilide due to residual water in solvent. Acetanilide was deprotonated and coordinated with the copper(I) centre to form a copper(I) amidate complex 3 when reacted in pre-dried solvent. In addition, a known complex 4, the oxidation product of dppf, was isolated from the same reaction system when reacted in air atmosphere. CV and TG experiments were carried out to check the electron transfer properties and thermal stabilities of complexes 2-3. Finally, the arylation reaction of complex 3 with iodobenzene was performed to study the reaction mechanism of copper(I) catalyzed Goldberg reaction.
- Liu, Xinfang,Zhang, Songlin,Ding, Yuqiang
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p. 185 - 189
(2012/07/14)
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- Pd(II)-catalyzed intramolecular C-H activation/C-C cross coupling for the synthesis of carbazoles from diaryl acetamides
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Pd(II)-catalyzed intramolecular C-H activation/C-C cross coupling within N,N-diphenyl-acetamides allows the efficient formation of differently substituted carbazoles. In this cross-dehydrogenative coupling, many different functional groups are tolerated and the starting material N,N-diphenyl- acetamides can be easily prepared in one step from commercially available acetanilides and iodobenzenes.
- Wang, Sichang,Mao, Hui,Ni, Zhangqin,Pan, Yuanjiang
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supporting information; experimental part
p. 505 - 508
(2012/02/01)
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- Solvent free, highly chemoselective N and O-acylation on silica and silica magnesium oxide: A recyclable solid surface
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Silica or silica/magnesium oxide mixed surface mediates the N and O-acylation, benzoylation or sulfonylation of hosts of substrates under solvent free conditions at ambient temperature with high chemoselectivity.
- Ghosh, Pranab,Mandal, Amitava
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p. 261 - 268
(2012/10/29)
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- Amorphous carbon-silica composites bearing sulfonic acid as solid acid catalysts for the chemoselective protection of aldehydes as 1,1-diacetates and for N-, O- and S-acylations
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Amorphous carbon-silica composites bearing sulfonic acid derived from inexpensive natural organic compounds (glucose, maltose, cellulose, chitosan and starch) were prepared by partial carbonization followed by sulfonation and their catalytic activity was evaluated for the protection of aldehydes as 1,1-diacetates and for N-, O- and S-acylations under solvent-free conditions. Different biomaterials have been chosen, with a view to select the most active solid acid catalyst. Carbon-silica composites were characterized by FTIR, XRD and elemental analysis. Sulfonated carbon-silica composite derived from starch was found to be the most active and could be recycled for several runs without loss of significant activity. It was also characterized by TGA, SEM and TEM.
- Gupta, Princy,Paul, Satya
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experimental part
p. 2365 - 2372
(2011/10/31)
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- Iron-doped single-walled carbon nanotubes as new heterogeneous and highly efficient catalyst for acylation of alcohols, phenols, carboxylic acids and amines under solvent-free conditions
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Iron-doped single-walled carbon nanotubes (Fe/SWCNTs) represent an efficient and new heterogeneous reusable catalyst for the acylation of a variety of alcohols, phenols, carboxylic acids and amines with acid chlorides or acid anhydrides under solvent-free conditions. The reactions of various primary, secondary, tertiary, and benzylic alcohols, diols, phenols, as well as aromatic and aliphatic amines give acylated adducts in good to excellent yields.
- Sharghi, Hashem,Jokar, Mahboubeh,Doroodmand, Mohammad Mahdi
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experimental part
p. 426 - 442
(2011/04/15)
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- A facile N-arylation of acetanilides with arynes
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An efficient, mild and transition-metal-free method for the N-arylation of acetanilides, leading to a range of unsymmetrical diarylamine products is reported. Reactions of ortho-silylaryl triflates with acetanilides in the presence of tetrabutylammonium triphenyldifluorosilicate (TBAT) in toluene afforded the desired products in good to excellent yields. Regioselectivity was also observed when unsymmetrical aryne precursors were used.
- Haber, James C.,Lynch, Michael A.,Spring, Stacey L.,Pechulis, Anthony D.,Raker, Joseph,Wang, Yi
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experimental part
p. 5847 - 5850
(2011/12/03)
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- A simple copper-catalyzed synthesis of tertiary acyclic amides
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The N-arylation of aromatic and aliphatic secondary acyclic amides, known to be poor nucleophiles, has been accomplished using a simple and cheap copper catalytic system. The corresponding tertiary acyclic amides, which can be found in numerous biologically active compounds, have been obtained in good to excellent yields.
- Racine, Emilie,Monnier, Florian,Vors, Jean-Pierre,Taillefer, Marc
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supporting information; experimental part
p. 2818 - 2821
(2011/07/09)
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- Air-stable titanocene bis(perfluorooctanesulfonate) as a new catalyst for acylation of alcohols, phenols, thiols, and amines under solvent-free condition
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Air-stable titanocene bis(perfluorooctanesulfonate) [Cp2Ti(OSO2C8F17)2] that shows high Lewis acidity was prepared from Cp2TiCl2 and AgOSO2C8F17. The compound was characterized by different techniques, and examined as a catalyst for acylation reactions. It was found that using equimolar acetic anhydride as acetylating agent and under solvent-free condition, Cp2Ti(OSO2C8F17)2 exhibits high activity and selectivity in the acetylation of various alcohols, phenols, thiols, and amines. Also, good catalytic efficiency is observed in the acylation of 2-phenylethanol across various acylating reagents. The catalyst can be reused without loss of activity in a test of ten cycles. The Cp2Ti(OSO2C8F17)2 catalyst affords a simple, efficient and general method for the acylation of alcohols, phenols, thiols, and amines.
- Qiu, Renhua,Zhang, Guoping,Ren, Xiaofang,Xu, Xinhua,Yang, Ronghua,Luo, Shenglian,Yin, Shuangfeng
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experimental part
p. 1182 - 1188
(2010/06/13)
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- Metal acetate/metal oxide in acetic acid: An efficient reagent for the chemoselective N-acetylation of amines under green conditions
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The use of catalytic amount of metal acetate or metal oxide in acetic acid is a new and highly efficient acetylating system for chemoselective N-acetylation of primary and secondary amines in excellent yields under reflux condition. No other solvent is required. The noted features of this method include mild reaction conditions, use of innocuous reagents, excellent yields, convenient work-up, and reuse of catalyst.
- Brahmachari, Goutam,Laskar, Sujay,Sarkar, Sajal
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experimental part
p. 288 - 295
(2010/10/18)
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- Copper-catalyzed N-arylation of amides using (S)-N-methylpyrrolidine-2- carboxylate as the ligand
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(S)-N-methylpyrrolidine-2-carboxylate, a derivative of natural L-proline, was found to be an efficient ligand for the copper-catalyzed Goldberg-type N-arylation of amides with aryl halides under mild conditions. A variety of N-arylamides were synthesized in good to high yields.
- Wang, Chaoyu,Liu, Lijuan,Wang, Wei,Ma, Dong-Sheng,Zhang, Hua
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experimental part
p. 1154 - 1160
(2010/06/13)
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- A green approach to chemoselective N-acetylation of amines using catalytic amount of zinc acetate in acetic acid under microwave irradiation
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It has been found for the first time that zinc acetate alone can act as a selective A'-acetylating agent without any solvent under closed vessel microwave irradiation. It is also observed that the use of a catalytic amount of this reagent in acetic acid is sufficient enough for smooth running of A'-acetylation of a number of structurally diverse amines, and the reaction is chemoselective with respect to phenols, thiols, acids and alcohols. Herein is reported a simple, efficient, cost-effective and environmentally benign alternative method for chemoselective A'-acetylation of amines using catalytic amount of zinc acetate in acetic acid under microwave irradiation. The reaction procedure requires no other solvent, and is rapid with good to excellent yields.
- Brahmachari,Laskar,Sarkar
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experimental part
p. 1274 - 1281
(2010/12/24)
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- Synthesis and structure of an extremely air-stable binuclear hafnocene perfluorooctanesulfonate complex and its use in lewis acid-catalyzed reactions
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An extremely air-stable μ2-hydroxy-bridged binuclear hafonocene perfluorooctanesulfoante complex was successfully synthesized. This complex showed high catalytic efficiency in the esterification of alcohols, phenol, thiol, and amines, in the Friedel-Crafts acylation of alylaryl ethers, in the Mukaiyama aldol reaction, and in the allylation of aldehydes and could be reused.
- Qiu, Renhua,Zhang, Guoping,Zhu, Yuyang,Xu, Xinhua,Shao, Lingling,Li, Yinhui,An, Delie,Yin, Shuangfeng
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supporting information; scheme or table
p. 6488 - 6494
(2010/02/28)
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- Mild and useful method for n-acylation of amines
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Iodine is found to promote quantitative N-acylation of primary and secondary amines (aliphatic and aromatic) in a very short time with an equimolar amount of acetyl chloride and benzoyl chloride under solvent-free conditions at room temperature. This catalytic acylation of amines offers an additional useful method for the acetylation using acetyl chloride instead of acetic anhydride and other acetylating agents. This method is also useful in the N-acylation of heterocycles. Mild reaction condition, high selectivity, efficiency, and good yields are some of the major advantages of the procedure.
- Phukan, Kandarpa,Ganguly, Mausumi,Devi, Nirada
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experimental part
p. 2694 - 2701
(2009/12/06)
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- Aryl halide tolerated electrophilic amination of arylboronic acids with N-chloroamides catalyzed by CuCl at room temperature
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(Chemical Equation Presented) N-Cl is no competition: Aryl halides were tolerated in an efficient ligandless CuCl-catalyzed electrophilic amination reaction of arylboronic acids with N-chloroamides (see scheme; Ac=acetoxy). This coupling proceeded smoothly at ambient temperature, and products were obtained with good to excellent yields.
- He, Chuan,Chen, Chong,Cheng, Jin,Liu, Chao,Liu, Wei,Li, Qiang,Lei, Aiwen
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supporting information; experimental part
p. 6414 - 6417
(2009/03/11)
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- Copper-catalyzed N-arylation of amides and azoles using phosphine-free hydrazone ligands
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Phosphine-free hydrazone such as 1c was found to be an efficient ligand for the copper-catalyzed Goldberg-type N-arylation of amides and Ullmann-type N-arylation of azoles with aryl halides under mild conditions. A variety of N-arylamides and N-arylazoles were synthesized in good to high yields. Georg Thieme Verlag Stuttgart.
- Mino, Takashi,Harada, Yoshikazu,Shindo, Hiroaki,Sakamoto, Masami,Fujita, Tsutomu
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p. 614 - 620
(2008/12/22)
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- Synthesis of diarylamines catalyzed by iron salts
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A study was conducted to demonstrate the synthesis of diarylamines catalyzed by iron salts. The study evaluated the influence acetyl as an N-protecting group. The coupling of acetanilide and iodobenzene was selected as a model reaction, to optimize the reaction conditions. It was observed that a considerable amount of the N-deprotected compound was obtained along with the desired N-acetyl diarylamine. It was also observed that diphenylamine was isolated in a significant yield, by performing a basic hydrolysis with NaOMe after the iron-catalyzed arylation. A one-pot synthesis of diphenylamine was performed by adding NaOMe to the N-arylation reaction mixture, after the acetanilide was consumed completely. It was demonstrated that the strategy overcomes the synthetic limitations associated with poor reactivity of aromatic amines under iron catalysis and serves as an alternative approach for the preparation of diarylamines.
- Correa, Arkaitz,Carril, Monica,Bolm, Carsten
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supporting information; experimental part
p. 10919 - 10922
(2009/11/30)
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- Copper-catalyzed amidation of aryl iodides in the presence of various chelating ligands
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N,N′-Dibenzylethylenediamine is presented as a new, efficient, and versatile bidentate ligand suitable for the copper catalyzed formation of the C-N bond. This bidentate ligand has been demonstrated to facilitate the copper catalyzed cross-coupling reactions of aryl iodides with amides to afford the desired products in good to excellent yields.
- Hosseinzadeh, Rahman,Golchoubian, Hamid,Masoudi, Mahtab
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experimental part
p. 649 - 653
(2009/05/11)
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- Design and syntheses of some new diphenylaminoisoxazolines as potent anti-inflammatory agent
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In the present investigation, a QSAR study is performed on twenty diphenylamino-2-isoxazoline derivatives using modified version of Allinger MM2 force field in Chem3D ultra structural descriptors. The relationship between anti-inflammatory activity and various descriptors is established by stepwise multiple regression analysis. The analyses have produced well predictive and statistically significant QSAR models which are further cross validated. This study helps to design some expectedly potent compounds and synthesized, accordingly. These compounds are auxiliary screened spectroscopically and tested for anti-inflammatory activity. All compounds have showed better activity when compared with ibuprofen as standard. These compounds are further subjected to ulceration studies showing good results with almost no ulcerogenic activity.
- Dravyakar,Kawade,Khedekar,Bhusari
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experimental part
p. 1559 - 1567
(2009/04/07)
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- Additive-free chemoselective acylation of amines and thiols
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Amines with different stereoelectronic nature were efficiently acylated at room temperature using acetic anhydride in the presence of no solvent or additive. Various thiols also react equally well under the same conditions. Chemoselective protection of amines in the presence of thiols, alcohols, and phenols and of thiols in the presence of alcohols, and phenols were achieved using competitive experiments.
- Mojtahedi, Mohammad M.,Saeed Abaee,Heravi, Majid M.,Behbahani, Farahnaz K.
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- Ruthenium(III) acetylacetonate [Ru(acac)3] -An efficient recyclable catalyst for the acetylation of phenols, alcohols, and amines under neat conditions
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A catalytic amount of ruthenium(III) acetylacetonate (2 mol%) [Ru(acac)3] enables solvent-free acetylation of phenols, alcohols, and amines at ambient temperature in good to excellent yields. Furthermore, the catalyst could be recovered and reused at least three times without a significant loss in yields.
- Varala, Ravi,Nasreen, Aayesha,Adapa, Srinivas R.
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p. 148 - 152
(2008/02/11)
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- An efficient synthesis of amides and esters via triacyloxyboranes
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Borane-tetrahydrofuran complex or borane-methyl sulfide complex is used to activate carboxylic acids to generate triacyloxyboranes. The triacyloxyboranes can be effectively reacted with various nucleophiles including alkylamines, arylamines, hydrazides, alcohols and phenols at reflux in toluene to provide the corresponding amides and esters in excellent yield. Aliphatic carboxylic acids are selectively esterified in the presence of aromatic carboxylic acids under the borane conditions. Georg Thieme Verlag Stuttgart.
- Huang, Zhongping,Reilly, John E.,Buckle, Ronald N.
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p. 1026 - 1030
(2008/02/13)
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- Organometallic chemistry of amidate complexes. Accelerating effect of bidentate ligands on the reductive elimination of N-aryl amidates from palladium(II)
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We report a series of arylpalladium complexes of acetamidate, sulfonamidate, and deprotonated oxazolidinone ligands that undergo reductive elimination with rates and yields that depend on the binding mode of the ancillary and amidate ligands. Complexes of the acetamidate ligands containing the bidentate phosphines DPPF and Xantphos as ancillary ligands undergo reductive elimination. The rate and yield were higher from the complex ligated by Xantphos, which contains a larger bite angle. In contrast, the analogous amidate complex containing a single sterically hindered monodentate ligand and a κ2-bound amidate ligand does not undergo reductive elimination. This trend of faster reductive elimination from complexes containing bidentate ancillary ligands than from a complex with a single monodentate ancillary ligand is unusual and is consistent with an effect of the denticity of the ancillary ligand on the binding mode of the amidate. Complexes of sulfonamidate ligands underwent reductive elimination faster than complexes of acetamidates, and reductive elimination occurred from complexes containing both bidentate and monodentate ancillary ligands. Like reductive elimination from the acetamidate complexes, reductive eliminations from the sulfonamidate complexes were faster when the complexes possessed bidentate Xantphos and κ1-sulfonamidate ligands. Copyright
- Fujita, Ken-Ichi,Yamashita, Makoto,Puschmann, Florian,Alvarez-Falcon, Miguel Martinez,Incarvito, Christopher D.,Hartwig, John F.
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p. 9044 - 9045
(2007/10/03)
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