- Design, synthesis and biological evaluation of novel α-acyloxy carboxamides via Passerini reaction as caspase 3/7 activators
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Evasion of apoptosis is a hallmark of cancer. Caspases; the key executors of apoptotic cascade are attractive targets for selective induction of apoptosis in cancer cells. Within this approach, various caspase activators were introduced as lead anticancer agents. In the current study, a new series of multifunctional Passerini products was synthesized and evaluated as potent caspase-dependent apoptotic inducers. The synthetic strategy adopted this isocyanide-based multicomponent reaction to possibly mimic the pharmacophoric features of various lead apoptotic inducers, where a series of α-acyloxy carboxamides was prepared from p-nitrophenyl isonitrile, cyclohexanone and various carboxylic acids. Accordingly, the main amide-based scaffold was decorated by substituents with varying nature and size to gain more information about structure-activity relationship. All the synthesized compounds were screened for cytotoxicity against normal human fibroblasts and their potential anticancer activities against three human cancer cell lines; MCF-7 (breast), NFS-60 (myeloid leukemia), and HepG-2 (liver) utilizing MTT assay. Among the most active compounds, 13, 21 and 22 were more potent and safer than doxorubicin with nanomolar IC50 values and promising selectivity indices. Mechanistically, 13, 21 and 22 induced apoptosis by significant caspase activation in all the screened cancer cell lines utilizing flow cytometric analysis and caspase 3/7 activation assay. Again, 13 and 21 recorded higher activation percentages than doxorubicin, while 22 showed comparable results. Apoptosis-inducing factor1 (AIF1) quantification assay declared that 13, 21 and 22 didn't mediate apoptosis through AIF1-dependent pathway (i.e. only by caspase activation). Physicochemical properties, pharmacokinetic profiles, ligand efficiency metrics and drug-likeness data of all the synthesized compounds were computationally predicted and showed that 13, 21 and 22 could be considered as drug-like candidates. Finally, selected compounds were preliminarily screened for possible antimicrobial activities searching for dual anticancer/antimicrobial agents as an advantageous approach for cancer therapy.
- Salah Ayoup, Mohammed,Wahby, Yasmin,Abdel-Hamid, Hamida,Ramadan, El Sayed,Teleb, Mohamed,Abu-Serie, Marwa M.,Noby, Ahmed
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Read Online
- Microwave promoted energy-efficient N-formylation with aqueous formic acid
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Microwave-induced organic reaction enhancement ('MORE') chemistry technique (open vessel; controlled microwave energy to stay below the boiling point of the reaction mixture) was used for the N-formylation of aliphatic and aromatic amines and amino heterocycles with aq formic acid (80%) on a multiple gram scale in a few minutes.
- Bose, Ajay K.,Ganguly, Subhendu N.,Manhas, Maghar S.,Guha, Atri,Pombo-Villars, Esteban
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- p-Nitrophenyl isocyanide
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Achiral p-nitrophenyl isocyanide, C7H4N 2O2, crystallizes in the orthorhombic chiral space group P212121. Attractive intermolecular interactions between the nitro O atoms and both aromatic H and nitro N atoms of neighbouring molecules are observed. The O...N interaction is surprisingly strong [N...O = 2.869 (2) A] compared with other aromatic nitro compounds.
- Zeller, Matthias,Hunter, Allen D.
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Read Online
- Hydrogen bonding in aromatic formamides
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The solid state structures of two p-substituted aromatic formamides have been determined. p-Nitro formamido benzene (1) crystallizes in the monoclinic space group C2/c with a = 10.9859(7), b = 10.0576(7), c = 13.0331(9) A, β = 97.148(1)° and Z = 8. p-formamido anisole (2) crystallizes in the orthorhombic space group Pna21 with a = 10.5598(7), b = 7.6553(5), c = 9.2522(6) A and Z = 4. Both compounds show hydrogen bonding in the solid state, forming infinite chains via N-H...O = C bridges. For the anisole formamide (2), the molecules exhibit in a zig-zag arrangement. The nitro compound (1) exhibits a spiral-like wavy line with a fourfold repeating unit, making it the first formamide having a chiral N-H...O bridged chain reminiscent of those found for α-helices in proteins. While the individual spirals of 1 are orientated either clockwise or counterclockwise, their orientation towards each other is random.
- Zeller, Matthias,Wilcox, Robert J.,Snyder III, Floyd G.,Seibel II, Harry A.,Takas, Nathan J.,Hunter, Allen D.
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- One-pot synthesis of 3-(2-cyanophenyl)quinazolin-4(3h)-one
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Anthranilonitrile reacting with formic acid at room temperature for three days gave 64% of 3-(2-cyanophenyl)quinazolin-4(3H)-one. Under similar conditions anthranilic acid, 4-nitroaniline, and 2,5-dichloroaniline were N-formylated in good yields.
- Szczepankiewicz,Suwinski
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Read Online
- Enantioselective Synthesis of Azetidines through [3 + 1]-Cycloaddition of Donor-Acceptor Aziridines with Isocyanides
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The enantioselective [3 + 1]-cycloaddition of racemic donor-acceptor (D-A) aziridines with isocyanides was first realized under mild reaction conditions using a chiral N,N′-dioxide/MgIIcomplex as catalyst, providing a facile route to enantioenriched exo-imido azetidines with good to excellent yield (up to 99%) and enantioselectivity (up to 94% ee). An obvious chiral amplification effect was observed in this system, and an explanation was elucidated based on the experimental investigation and X-ray crystal structure of the enantiomerically pure catalyst.
- Zhang, Fengcai,Sang, Xinpeng,Zhou, Yuqiao,Cao, Weidi,Feng, Xiaoming
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supporting information
p. 1513 - 1517
(2022/03/01)
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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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- Functionalizing HY zeolite with sulfonic acid, a micro-meso structure reusable catalyst for organic transformations
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A new class of sulfonic acid functionalized HY zeolite (HY-N-SA) catalyst has been prepared and characterized by some method such as XRD, FT-IR, FESEM, TEM, TGA, NH3-TPD and N2 physisorption. The result shows the micro-meso structure for catalyst without ordering in the mesophase. Then, the HY-N-SA micro-meso structure was used as an acidic catalyst to synthesize of coumarins via Pechmann reaction and facile transformation of amines to formamides under solvent-free condition. To consider the effect of acidity and kind and size of porous on the catalyst activity, this catalyst was compared with NaY-N-SA and MCM-N-SA and pure porous material (NaY and MCM-41). The significant advantages of HY-N-SA with respect to other catalysts are short reaction times, high yields, pure products, mild conditions and easy work-up. In addition, we report an original and environmentally friendly solvent-free procedure which reusability of catalyst makes this method nearly green and environmentally friendly.
- Tavakoli, Fatemeh,Zendehdel, Mojgan
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- Small molecule microarray identifies inhibitors of tyrosyl-DNA phosphodiesterase 1 that simultaneously access the catalytic pocket and two substrate binding sites
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Tyrosyl-DNA phosphodiesterase 1 (TDP1) is a member of the phospholipase D family of enzymes, which catalyzes the removal of both 3′- and 5′-DNA phosphodiester adducts. Importantly, it is capable of reducing the anticancer effects of type I topoisomerase (TOP1) inhibitors by repairing the stalled covalent complexes of TOP1 with DNA. It achieves this by promoting the hydrolysis of the phosphodiester bond between the Y723 residue of human TOP1 and the 3′-phosphate of its DNA substrate. Blocking TDP1 function is an attractive means of enhancing the efficacy of TOP1 inhibitors and overcoming drug resistance. Previously, we reported the use of an X-ray crystallographic screen of more than 600 fragments to identify small molecule variations on phthalic acid and hydroxyquinoline motifs that bind within the TDP1 catalytic pocket. Yet, the majority of these compounds showed limited (millimolar) TDP1 inhibitory potencies. We now report examining a 21?000-member library of drug-like Small Molecules in Microarray (SMM) format for their ability to bind Alexa Fluor 647 (AF647)-labeled TDP1. The screen identified structurally similarN,2-diphenylimidazo[1,2-a]pyrazin-3-amines as TDP1 binders and catalytic inhibitors. We then explored the core heterocycle skeleton using one-pot Groebke-Blackburn-Bienayme multicomponent reactions and arrived at analogs having higher inhibitory potencies. Solving TDP1 co-crystal structures of a subset of compounds showed their binding at the TDP1 catalytic site, while mimicking substrate interactions. Although our original fragment screen differed significantly from the current microarray protocol, both methods identified ligand-protein interactions containing highly similar elements. Importantly inhibitors identified through the SMM approach show competitive inhibition against TDP1 and access the catalytic phosphate-binding pocket, while simultaneously providing extensions into both the substrate DNA and peptide-binding channels. As such, they represent a platform for further elaboration of trivalent ligands, that could serve as a new genre of potent TDP1 inhibitors.
- Zhao, Xue Zhi,Kiselev, Evgeny,Lountos, George T.,Wang, Wenjie,Tropea, Joseph E.,Needle, Danielle,Hilimire, Thomas A.,Schneekloth, John S.,Waugh, David S.,Pommier, Yves,Burke, Terrence R.
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p. 3876 - 3884
(2021/04/02)
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- DMF·HCl as a versatile and straightforward N- and O-formylating agent
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Inspired by the serendipitous isolation of N-formylpiperazines when we attempted the synthesis of a series of piperazines, we have developed a straightforward methodology for the N- and O- formylation of secondary cyclic amines, anilines and steroids, respectively. Such approach is based on the hitherto non-reported use of DMF·HCl complex, as a versatile and easily-available formylating system that can be stored without apparent loss of activity.
- Ramírez-Vázquez, Dulce G.,Vi?as-Bravo, Omar,Martínez-Pascual, Roxana,Pérez-Picaso, Lemuel,Castro-Cerritos, Karla Viridiana
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supporting information
p. 585 - 592
(2020/11/19)
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- Borane-Trimethylamine Complex as a Reducing Agent for Selective Methylation and Formylation of Amines with CO2
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We report herein that a borane-trimethylamine complex worked as an efficient reducing agent for the selective methylation and formylation of amines with 1 atm CO2 under metal-free conditions. 6-Amino-2-picoline serves as a highly efficient catalyst for the methylation of various secondary amines, whereas in its absence, the formylation of primary and secondary amines was achieved in high yield with high chemoselectivity. Mechanistic studies suggest that the 6-amino-2-picoline-borane catalytic system operates like an intramolecular frustrated Lewis pair to activate CO2.
- Zhang, Yanmeng,Zhang, He,Gao, Ke
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supporting information
p. 8282 - 8286
(2021/10/25)
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- Silver-Catalyzed Selective Multicomponent Coupling Reactions of Arynes with Nitriles and Isonitriles
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Pathway selective aryne-based novel multicomponent coupling reactions with isonitriles and nitriles are described. Crucial to these reactions is the formation of a silver-aryne complex, which shows differential reactivity toward isonitriles and nitriles to form two different forms of ortho-nitrilium organosilver arene species. Interception of the nitrilium of an aryne-isonitrile adduct with another isonitrile leads to the formation of benzocyclobutene-1,2-diimines, whereas the nitrilium of an aryne-nitrile adduct renders selective formation of 3H-indol-3-imines or 3-iminoindolin-2-ol depending on the structure of the nitrile employed.
- Ghorai, Sourav,Lin, Yongjia,Xia, Yuanzhi,Wink, Donald J.,Lee, Daesung
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supporting information
p. 642 - 647
(2020/01/31)
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- Mild C?F Activation in Perfluorinated Arenes through Photosensitized Insertion of Isonitriles at 350 nm
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Fluorinated compounds have become important in the fields of agrochemical industry, pharmaceutical chemistry and materials sciences. Accordingly, various methods for their preparation have been developed in the past. Fluorinated compounds can be accessed via conjugation with fluorinated building blocks, via C?H fluorination or via selective activation of perfluorinated compounds to give the partially fluorinated congeners. Especially the direct activation of C?F bonds, one of the strongest σ-bonds, still remains challenging and new strategies for C?F activation are desirable. Herein a method for the photochemical activation of aromatic C?F bonds is presented. It is shown that isonitriles selectively insert into aromatic C?F bonds while aliphatic C?F bonds remain unaffected. Mechanistic studies reveal the reaction to proceed via the indirect excitation of the isonitrile to its triplet state by photoexcited acetophenone at 350 nm. Due to the relatively mild light used, the process shows high functional group tolerance and various compounds of the class of benzimidoyl fluorides are accessible from aryl isonitriles and commercially available perfluorinated arenes. (Figure presented.).
- Weidlich, Frauke,Esumi, Naoto,Chen, Dongyang,Mück-Lichtenfeld, Christian,Zysman-Colman, Eli,Studer, Armido
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supporting information
p. 376 - 383
(2019/11/19)
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- A NHC-silyliumylidene cation for catalytic N?formylation of amines using carbon dioxide
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This study describes the use of a silicon(II) complex, namely, the NHC-silyliumylidene cation complex [(IMe)2SiH]I (1, IMe =:C{N(Me)C(Me)}2), to catalyze the chemoselective N-formylation of primary and secondary amines using CO2 and PhSiH3 under mild conditions to afford the corresponding formamides as a sole product (average reaction time: 4.5 h; primary amines, average yield: 95%, average TOF: 8 h?1; secondary amines, average yield: 98%, average TOF: 17 h?1). The activity of 1 and product yields outperform the currently available non-transition-metal catalysts used for this catalysis. Mechanistic studies show that the silicon(II) center in complex 1 catalyzes the C?N bond formation via a different pathway in comparison with non-transition-metal catalysts. It sequentially activates CO2, PhSiH3, and amines, which proceeds via a dihydrogen elimination mechanism, to form formamides, siloxanes, and dihydrogen gas.
- Leong, Bi-Xiang,Teo, Yeow-Chuan,Condamines, Cloe,Yang, Ming-Chung,Su, Ming-Der,So, Cheuk-Wai
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p. 14824 - 14833
(2020/12/21)
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- N,N-coordinated palladium complex with meta-carborane ligand and preparation and application of palladium complex
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The invention relates to an N,N-coordinated palladium complex with a meta-carborane ligand and preparation and application of the palladium complex. A preparation method of the palladium complex comprises the following steps that (1) an n-BuLi solution is added into a meta-carborane solution and then a reaction is performed at a room temperature for 30-60 min; (2) 3-chloromethylpyridine is added and reacts at the room temperature for 3-5 h; (3) PdCl2 is added and reacts at the room temperature for 2-5 h, and the palladium complex is obtained through post-treatment; and the palladium complex isused for catalyzing an arylamine formylation reaction to prepare an arylamine formamide compound. Compared with the prior art, the synthesis process of the palladium complex is simple and green, andhas excellent selectivity and a high yield; and the palladium complex has the characteristics such as stable physicochemical properties and thermal stability, and exhibits excellent catalytic activityin the arylamine formylation reaction.
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Paragraph 0053-0056
(2019/11/12)
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- KOtBu-Promoted Transition-Metal-Free Transamidation of Primary and Tertiary Amides with Amines
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This work discloses transamidation of primary and tertiary amides with a range of aryl, heteroaryl, and aliphatic amines using potassium tert-butoxide. The reaction proceeds at room temperature under transition-metal-free conditions providing secondary amides in high yields. Moreover, reaction of cyclopropyl amine with tertiary amides proceeds with ring-opening to provide a rapid access to enamides.
- Ghosh, Tridev,Jana, Snehasish,Dash, Jyotirmayee
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supporting information
p. 6690 - 6694
(2019/09/12)
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- Mesostructure organic-inorganic hybrid ionic liquids based on heteropoly acids: Effect of linkage on the molecular structure and catalytic activity
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The new inorganic–organic hybrids based on SO3H-functionalized ionic liquids (ILs) and Keggin-type heteropoly acids (H3PW12O40, H3PMo12O40, and H4SiW12O40; HPAs) are prepared and characterized by FT-IR, NMR, XRD, CV, SEM/EDX, ICP-OES, BJH and UV. Different molecular structures according to the different inorganic part were also proved. Potentiometric titration showed a good relationship between catalytic activity and acidity of the catalysts. Electrochemical aspects showed electron transfer ability of the compounds. For understanding catalytic activities of the HPA-IL hybrids in N-formylation reaction, effect of catalyst composition, substrate, and reaction conditions were studied. The best SO3H-functionalized ionic liquid catalyst was readily recovered and reused for four runs. Easy preparation of the catalyst, simple and easy work-up, mild reaction conditions, low cost, excellent yields and short reaction times are the key features of this work.
- Shahebrahimi, Shabnam,Rafiee, Ezzat,Sadrjavadi, Komail
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- Palladium-Catalyzed Diarylation of Isocyanides with Tetraarylleads for the Selective Synthesis of Imines and α-Diimines
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Using tetraaryllead compounds (PbAr4) as arylating reagents, isocyanides undergo selective diarylation in the presence of palladium catalysts such as Pd(OAc)2 or Pd(PPh3)4 to afford imines and/or α-diimines based on the isocyanide employed. With aliphatic isocyanides, imines are obtained preferentially, whereas α-diimines are formed in the case of electron-rich aromatic isocyanides. The differences in imine/α-diimine selectivity can be attributed to the stability of imidoylpalladium intermediates formed in this catalytic reaction. Compared with other arylating reagents, tetraaryllead compounds are excellent candidates for use in the selective transformations to imines and/or α-diimines, especially in terms of inhibiting the oligomerization of isocyanides, which results in a lower product selectivity in many transition-metal-catalyzed reactions of isocyanides.
- Tran, Cong Chi,Kawaguchi, Shin-Ichi,Kobiki, Yohsuke,Matsubara, Hitomi,Tran, Dat Phuc,Kodama, Shintaro,Nomoto, Akihiro,Ogawa, Akiya
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p. 11741 - 11751
(2019/10/02)
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- Synthesis of Imides, Imidates, Amidines, and Amides by Intercepting the Aryne-Isocyanide Adduct with Weak Nucleophiles
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New aryne-based multicomponent coupling reactions for the formation of functionalized aromatic compounds have been developed. Arynes generated from triynes or tetraynes through the hexadehydro Diels-Alder reaction readily react with isocyanide to generate nitrilium intermediate. Intercepting this nitrilium species with various weak nucleophile including carboxylic acids, alcohols, sulfonamides, or water generated the corresponding imides, imidates, amidines, or amides. The high regioselectivity of these transformations was mainly controlled by the substituents of the arynes.
- Ghorai, Sourav,Lee, Daesung
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supporting information
p. 7390 - 7393
(2019/10/02)
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- Mild and facile synthesis of formamide: Reduction and functionalization of CO2 using NaBH(OAc)3 under atmospheric pressure
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An approach for N-formylation of amines was developed using NaBH(OAc)3 as a reductant under an atmospheric pressure of CO2 at 50 °C. The corresponding formylated products of various amines, including aliphatic and aromatic amines, amines with reductive-sensitive nitro groups and alkynyl groups and benzamides were obtained in good to excellent yields, and the possible reaction mechanism was also proposed.
- Liu, Huan,Nie, Zhuang,Shao, Jiaan,Chen, Wenteng,Yu, Yongping
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supporting information
p. 3552 - 3555
(2019/07/09)
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- Catalyst-Free Transamidation of Aromatic Amines with Formamide Derivatives and Tertiary Amides with Aliphatic Amines
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A simple catalyst- and promoter-free protocol has been developed for the transamidation of weakly nucleophilic aromatic amines with formamide derivatives and low-reactivity tertiary amides with aliphatic amines. This strategy is advantageous because no catalyst or promoters are needed, no additives are required, separation and purification is easy, and the reaction is scalable. Significantly, this strategy was further applied to synthesize several pharmaceutical molecules on a gram scale, and excellent yields were achieved.
- Yin, Jiawen,Zhang, Jingyu,Cai, Changqun,Deng, Guo-Jun,Gong, Hang
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supporting information
p. 387 - 392
(2019/01/11)
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- Electrochemical N -Formylation of Amines via Decarboxylation of Glyoxylic Acid
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A new method for the synthesis of formamides has been developed through electrochemical decarboxylative N-formylation of amines with glyoxylic acid. This protocol provides an efficient approach to formamides with a broad range of functional group tolerance under ambient conditions.
- Lin, Dian-Zhao,Huang, Jing-Mei
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supporting information
p. 2112 - 2115
(2018/04/14)
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- Selective Gold-Catalysed Synthesis of Cyanamides and 1-Substituted 1H-Tetrazol-5-Amines from Isocyanides
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The newly discovered gold-catalysed reaction of isocyanides with hydrazoic acid generated in situ from trimethylsilyl azide and methanol (or, alternatively, from NaN3/AcOH) produces either cyanamides or 1-substituted 1H-tetrazol-5-amines, depending on the amount of available HN3. The reaction proceeds selectively and in generally high yields of either product, thus providing a particularly convenient access to a wide range of substituted 1H-tetrazol-5-amines that are rather difficult to access otherwise.
- ?koch, Karel,Císa?ová, Ivana,?těpni?ka, Petr
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supporting information
p. 13788 - 13791
(2018/09/14)
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- TEMPO-Catalyzed Aerobic Oxidative Selenium Insertion Reaction: Synthesis of 3-Selenylindole Derivatives by Multicomponent Reaction of Isocyanides, Selenium Powder, Amines, and Indoles under Transition-Metal-Free Conditions
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A novel and efficient approach for the selenium functionalization of indoles was developed with selenium powder as the selenium source, catalyzed by 2,2,6,6-tetramethylpiperidinooxy (TEMPO) and employing O2 as the green oxidant. This protocol provides a practical route for the synthesis of 3-selenylindole derivatives and has the advantages of readily available starting materials, mild reaction conditions, and a wide scope of substrates. Electron spin-resonance (ESR) studies reveal that the approach involves the formation of nitrogen-centered radicals and selenium radicals via oxidation of in situ generated selenoates.
- Liu, Huan,Fang, Yi,Wang, Shun-Yi,Ji, Shun-Jun
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supporting information
p. 930 - 933
(2018/02/22)
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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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- Mesoporous silica SBA-15 functionalized with acidic deep eutectic solvent: A highly active heterogeneous N-formylation catalyst under solvent-free conditions
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Mesoporous silica SBA-15 functionalized with N-methylpyrrolidonium-zinc chloride based deep eutectic solvent (DES) is found to be a more efficient and reusable catalyst for a convenient N-formylation of a variety of amines at room temperature. N-Formylation of primary, secondary as well as heterocyclic amines have been carried out in good to excellent yields by treatment with formic acid in low loading of DES/SBA-15 an environmentally benign catalyst for the first time. The DES/SBA-15 catalyst, which possesses both Br?nsted and Lewis acidities as well as an active SBA-15 support, makes this procedure quite simple, reusable, more convenient and practical. This catalyst was tolerant of a wide range of functional groups, and it can be reused for four runs without obvious deactivation.
- Azizi, Najmedin,Edrisi, Mahtab,Abbasi, Faezeh
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- One-step synthesis of N, N′-substituted 4-imidazolidinones by an isocyanide-based pseudo-five-multicomponent reaction
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A pseudo-five-multicomponent reaction involving an isocyanide, a primary amine, two molecules of formaldehyde and water is reported, which gives N,N′-substituted 4-imidazolidinones when trifluoroethanol is used as the solvent. The reaction proceeds with good yields and with a wide variety of amines and isocyanides, providing an efficient new entry to these heterocycles. A preliminary study of the reaction mechanism suggests that trifluoroethanol, although acting as the solvent, is directly involved as a reagent in the reaction pathway.
- Attorresi, Cecilia I.,Bonifazi, Evelyn L.,Ramírez, Javier A.,Gola, Gabriel F.
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supporting information
p. 8944 - 8949
(2018/12/10)
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- Method for synthesizing formamide compound
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The invention discloses a method for synthesizing a formamide compound. The synthetic method comprises the following steps: taking carbamyl imidazole compound as a raw material, preparing the formamide compound in a mixed solution of tetrahydrofuran and water by taking hydroboron as a reducing agent. The catalyst hydroboron used in the method disclosed by the invention has the advantages of environment friendliness, stable performance, high conversion rate and the like. Moreover, the initial raw material and used reagents are simple and readily available, the cost is low, and the operation is simple and feasible. Therefore, the route is a route which is low in cost, simple in operation and suitable for industrial production.
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Paragraph 0048-0050
(2017/09/01)
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- An efficient reduction of N-substituted carbonylimidazolides into formamides by NaBH4
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A novel, simple and versatile protocol was investigated for highly efficient synthesis of formamides through reducing N-substituted carbonylimidazolides by NaBH4 under mild reaction conditions. By this method, not only carboxylic acids or isocyanates, but also amines can readily access formamides with high yields.
- Chen, Zhiyong,Cao, Yiming,Tian, Zeyu,Zhou, Xuan,Xu, Wenjin,Yang, Jia,Teng, Hanbing
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p. 2166 - 2170
(2017/05/10)
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- Development of an Industrial Process Based on the Groebke-Blackburn-Bienaymé Multicomponent Reaction: Efficient Preparation- of 3-Aminoimidazo[1,2-a]pyrazines
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3-Aminoimidazo[1,2-a]pyrazine is an important scaffold that is found in many drugs. This scaffold is rapidly accessible through a Groebke-Blackburn-Bienaymé cyclisation starting from an aminopyrazine, an aldehyde and an isocyanide. A scale-up process of this multicomponent reaction has been achieved in high yield and with excellent purity. The scope and limitations of this process leading to various 3-aminoimidazo[1,2-a]pyrazines are disclosed.
- Baenziger, Markus,Durantie, Estelle,Mathes, Christian
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supporting information
p. 2266 - 2274
(2017/05/05)
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- Novel method for synthesizing N-substitute amide derivative
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The invention discloses a novel method for synthesizing an N-substitute amide derivative. The novel method is characterized by comprising the steps that at the air atmosphere, no catalyst or alkali or other any additives are added, an organic amine compound shown in a formula (I) is adopted as a reaction substrate, a solvent shown in a formula (II) is adopted as an acylation reagent, an acylation reaction is performed under the reaction temperature of 120-150 DEG C to generate the N-substitute amide derivative shown in a formula (III), and the equation is shown in the description. The novel method has the advantages that environmental protection is achieved, and post-treatment and product separation are easy; the range of the substrate is wide, and the substrate can be primary amine and can also be secondary amine; the solvent can be amide and can also be carboxylic acid, and the solvent can be adopted as the acylation reagent to participate in the reaction; the reaction efficiency is high, and the majority of reactions can reach the quantified yield; water and air have no effect on the reaction, inert gas shielding is not needed, and operation is easy.
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Paragraph 0035; 0036; 0037; 0038; 0039; 0040-0041; 0116-0118
(2017/09/02)
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- Aerobic radical-cascade cycloaddition of isocyanides, selenium and imidamides: Facile access to 1,2,4-selenadiazoles under metal-free conditions
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A novel and facile metal-free method for the green synthesis of 1,2,4-selenadiazol-5-amine derivatives through the aerobic radical-cascade multi-component reactions of isocyanides, selenium powder and imidamides is reported herein. O2 in the air was employed as the green oxidant to achieve the cycloaddition with the generation of H2O as the sole by-product. It also features good functional group compatibility and broad substrate scope. In addition, this method was successfully applied to the functionalization of biologically active molecules.
- Fang, Yi,Zhu, Zheng-Lin,Xu, Pei,Wang, Shun-Yi,Ji, Shun-Jun
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supporting information
p. 1613 - 1618
(2017/06/05)
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- Cobalt(II)-Catalyzed Isocyanide Insertion Reaction with Sulfonyl Azides in Alcohols: Synthesis of Sulfonyl Isoureas
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A Co(II)-catalyzed isocyanide insertion reaction with sulfonyl azides in alcohols to form sulfonyl isoureas via nitrene intermediate has been developed. This protocol provides a new, environmentally friendly, and simple strategy for the synthesis of sulfonyl isourea derivatives by employing a range of substrates under mild conditions.
- Jiang, Tian,Gu, Zheng-Yang,Yin, Ling,Wang, Shun-Yi,Ji, Shun-Jun
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supporting information
p. 7913 - 7919
(2017/08/14)
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- A capable cobalt nano-catalyst for the N-formylation of various amines and its biological activity studies
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The Fe3O4 magnetic nanoparticles (Fe3O4 MNPs) were modified with 1,10-phenanthroline-5,6-diol and the relevant Co complex (Fe3O4@Phendiol@Co) synthesized as a nano-magnetic heterogeneous catalyst to be used for the N-formylation of various amines at room temperature under solvent-free conditions. Also, in order to find the better concept of the catalyst role, the N-formylation reaction was carried out by the use of ultrasound irradiation in the absence of the Co nano-catalyst and the results were compared. The catalyst characterized by different methods such as the elemental analysis (CHN), ICP, FT-IR, XRD, EDX, SEM, TEM, TG-DTA, VSM and XPS. In addition, the antioxidant and the antibacterial activities of the Fe3O4@Phendiol@Co nano-catalyst and its Phendiol ligand were in vitro screened by 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging and disc diffusion methods. Results showed that they possess strong antioxidant activity (IC50; 0.182?±?0.006?mg/ml) and good antibacterial potential in comparison to standards.
- Habibi, Davood,Heydari, Somayyeh,Afsharfarnia, Mina
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- NaY zeolite functionalized by sulfamic acid/Cu(OAc)2 as a new and reusable heterogeneous hybrid catalyst for efficient solvent-free formylation of amines
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NaY zeolite functionalized by sulfamic acid/Cu(OAc)2 [NaY/SA/Cu(II)] was synthesized and used as a new, efficient and recyclable catalyst for preparation of formamides. This novel organic-inorganic hybrid catalyst was characterized by several techniques such as FT-IR, XRD, SEM, EDX and TG analysis. Chemoselectivity, easy procedure, excellent yields, very short reaction times, solvent-free and mild reaction conditions are some benefits of this new protocol.
- Kazemi, Samira,Mobinikhaledi, Akbar,Zendehdel, Mojgan
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p. 1767 - 1772
(2017/07/27)
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- An imidazolium based ionic liquid supported on Fe3O4@SiO2 nanoparticles as an efficient heterogeneous catalyst for N-formylation of amines
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An imidazolium based ionic liquid, 1-methyl-3-(3-triethoxysilylpropyl) imidazolium chloride, could be immobilized on the surface of silica-coated ferrite nanoparticles (Fe3O4@SiO2-IL) and could be evaluated as a recyclable catalyst for the N-formylation of amines using formic acid under solvent-free conditions. The prepared organic-inorganic hybrid material could be characterized by various techniques such as Fourier Transform Infrared Spectroscopy (FT-IR), X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray Spectroscopy (EDS) and Vibrating Sample Magnetometer (VSM) studies. Utilizing the ferromagnetic nature of Fe3O4, the prepared catalyst could be easily recovered after completion of the reaction by using an external magnetic field. The catalyst could be reused for up to five runs with remarkable catalytic activity. The described methodology has various advantages when compared with other methods that rely on homogeneous catalysts.
- Garkoti, Charu,Shabir, Javaid,Mozumdar, Subho
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p. 9291 - 9298
(2017/08/29)
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- Solvent- and catalyst-free N-formylations of amines at ambient condition: Exploring the usability of aromatic formates as N-formylating agents
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A solvent- and catalyst-free N-formylation protocol has been developed for amines (1s–21s) where aromatic formates (1r–6r) were used as the N-formylating agents. The amine substrates include both primary and secondary aromatic amines (1s–19s) as well as aliphatic amine (20s) and a primary amide (21s). Structures of both the aromatic formate and amine components strongly influenced the rate of the reaction and yield of the N-formamide products. The reaction condition is mild and easy to operate. This protocol can be done smoothly under ambient conditions and gives high yield of formamide products. Furthermore, the present method cannot be applied for the formylation of thiol group (22s). This signifies its possible use for the chemoselective N-formylation of amine in the presence of thiol functionality.
- Batuta, Shaikh,Begum, Naznin Ara
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supporting information
p. 137 - 147
(2017/01/11)
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- New catalytic performance of immobilized sulfuric acid on activated charcoal for n-formylation of amines with ethyl formate
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Summary: Simple and highly efficient procedure for N-formylation of various amines was carried out in the presence of the immobilized sufuric acid on activated charcoal as an efficient promoter system. All reactions were taken place in refluxing ethyl formate (54 °C) under mild reaction conditions. The product formamides were obtained in high to excellent yields (83-95%) within 4-80 min.
- Abdollahi, Mohammad,Zeynizadeh, Behzad,Sadighnia, Leila
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p. 619 - 627
(2017/11/06)
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- Microwave-Assisted Formylations of Weakly Basic Anilines with Methyl Formate Catalyzed by Calcium and Hydrogen Triflimides
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Catalytic amounts of calcium and hydrogen triflimides [Ca(NTf2)2, HNTf2] were found to be efficient for the solvent-free formylation of a variety of weakly basic anilines by using cheap and widely available methyl formate as the formylating agent under microwave irradiation. Initial investigations showed that in the case of calcium triflimide, Br?nsted acid catalysis was most likely operating. Remarkably, the corresponding calcium triflate and triflic acid were significantly less active.
- Tan, Eric,Ung, Sosthène,Corbet, Matthieu
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supporting information
p. 1836 - 1840
(2016/05/09)
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- Acidic ionic liquid immobilized on nanoporous Na+-montmorillonite as an efficient and reusable catalyst for the formylation of amines and alcohols
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In this work, nanoporous sodium montmorillonite clay (Na+-MMT) was used as a support for the immobilization of 1-methyl-3-(trimethoxysilylpropyl)-imidazolium hydrogen sulfate. The Na+-MMT chemical modification ([Na+-MMT-[pmim]HSO4) was confirmed by a variety of techniques including Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy and potentiometric titration. The catalytic performance of this immobilized acidic ionic liquid was probed for the N-formylation of a variety of amines using formic acid under solvent-free conditions. This reagent is also useful for the formylation of benzylic alcohols. The procedure gave the products in excellent yields in very short reaction times. Also, this catalyst can be reused ten times without loss of its catalytic activity.
- Shirini, Farhad,Mazloumi, Masoumeh,Seddighi, Mohadeseh
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p. 1759 - 1776
(2016/03/16)
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- Selective formylation and methylation of amines using carbon dioxide and hydrosilane catalyzed by alkali-Metal carbonates
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The formylation and methylation of amines with carbon dioxide and hydrosilanes are emerging yet important types of transformations for CO2. Catalytic methods effective for both reactions with wide substrate scopes are rare because of the difficulty in controlling the selectivity. Herein, we report that simple and readily available inorganic bases alkali-metal carbonates, especially cesium carbonatecatalyze both the formylation and methylation reactions efficiently under mild conditions. The selectivity can be conveniently controlled by varying the reaction temperature and silane. A “cesium effect” on both reactions was observed by comparing the catalytic activity of various alkali-metal carbonates. Combined experimental and computational studies suggested the following reaction mechanism: (i) activation of Si?H by Cs2CO3, (ii) insertion of CO2 into Si?H, (iii) formylation of amines by silyl formate, and (iv) reduction of formamides to methylamines.
- Fang, Chi,Lu, Chunlei,Liu, Muhua,Zhu, Yiling,Fu, Yao,Lin, Bo-Lin
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p. 7876 - 7881
(2018/05/23)
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- A highly efficient magnetic solid acid nanocatalyst for the synthesis of new bulky heterocyclic compounds
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Fe3O4 nanoparticles were prepared and coated with 3-aminopropyltriethoxysilane (APTES). The formed amine-surfaced Fe3O4@APTES NPs were further chemically modified with maleic anhydride (MAH) to generate Fe3O4@APTES·MAH NPs. This catalyst was characterized by FT-IR, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TG), energy dispersive X-ray analyzer (EDAX), vibrating sample magnetometry (VSM) and the dynamic light scattering (DLS) measurement technique. The catalyst showed high thermal stability and good reusability. Some new bulky heterocyclic compounds such as bis(2,4,5-triarylimidazole), bis(1,4-dihydropyridine), bis(1,8-dioxooctahydroxanthene) and bis(1,8-dioxo-decahydroacridine) derivatives were synthesized using 4,4′-(alkylazanediyl)dibenzaldehyde as substrate and Fe3O4@APTES or Fe3O4@APTES·MAH as catalyst. The high purity products were isolated and the catalyst was easily separated with a simple work-up with magnetic field and was recycled several times without noticeable loss of reactivity under the described reaction conditions.
- Nasr-Esfahani, Masoud,Rafiee, Zahra,Montazerozohori, Morteza,Kashi, Hassan
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p. 47298 - 47313
(2016/06/06)
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- Transamidation of primary carboxamides, phthalimide, urea and thiourea with amines using Fe(OH)3@Fe3O4 magnetic nanoparticles as an efficient recyclable catalyst
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The highly efficient transamidation of primary amides, phthalimide, urea and thiourea with amines catalyzed by magnetic Fe(OH)3@Fe3O4 nanoparticles is described. This magnetic nanocomposite is able to catalyze transamidation reactions of a wide range of the above-mentioned substrates with amines, generating a new amide bond in moderate to good yields. The catalyst exhibited very good recyclability and reusability up to five runs without significant loss of its catalytic activity.
- Arefi, Marzban,Heydari, Akbar
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p. 24684 - 24689
(2016/03/16)
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- Covalently bonded zwitterionic sulfamic acid onto the SBA-15 (SBA-15/PrEn-NHSO3H) reveals good Bronsted acidity behavior and catalytic activity in N-formylation of amines
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Ethylenediamine-functionalization of SBA-15 with N1-(3-(trimethoxysilyl)propyl)ethane-1,2-diamine (PrEn) was then underwent covalent sulfonation over secondary and primary amine groups (SBA-15/PrEn-NHSO3H) on the surface of the mesoporous SBA-15 pore walls. Scanning electron microscope (SEM), transmission electron microscope (TEM), SEM-energy dispersive X-ray (SEM-EDX), BET surface are analysis, thermal gravimetric (TG), FT-IR spectrums and CHNS were recorded for the characterization of SBA-15/PrEn-NHSO3H. This material was studied as a novel catalyst for N-formylation of amines. Based on the results, SBA-15/PrEn-NHSO3H acted as zwitterionic IL-type heterogeneous catalyst with simple separation feature from the reaction mixture. Moreover, it exhibited excellent recyclability at least for 12 times, and a higher catalytic activity toward N-formylation.
- Rostamnia, Sadegh,Doustkhah, Esmail
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p. 317 - 324
(2015/11/28)
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- An efficient method for the synthesis of formamidine and formamide derivatives promoted by sulfonated rice husk ash (RHA-SO3H)
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A mild, simple and efficient method has been developed for the promotion of the preparation of N,N′-diphenylformamidines from various aromatic amines and ethyl orthoformate using sulfonated rice husk ash (RHA-SO3H) solid acid catalyst. This reagent has also been used for the N-formylation of a variety of amines using formic acid under solvent-free conditions. The procedures gave the products in very short reaction times and good-to-high yields. Also this catalyst can be reused for five times without loss of its catalytic activity.
- Seddighi, Mohadeseh,Shirini, Farhad,Mamaghani, Manouchehr
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p. 433 - 439
(2015/02/05)
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- Regiochemistry of nucleophilic substitution of pentachloropyridine with N and O bidentate nucleophiles
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Site reactivity of some enol-imines derived from N-aryl formamides with pentachloropyridine under basic conditions in dry CH3CN was investigated. The aromatic nucleophilic substitution of pentachloropyridine with enol-imines occurs at the 4-position of pyridine ring by both oxygen and nitrogen site of enol-imines. Nucleophilic attack by the oxygen of enol-imine gave corresponding oximino compounds as a mixture of E- and Z-isomers. In contrast, nucleophilic attack by the nitrogen of enol-imine gave the unexpected N,N-di-substituted aryl compounds. The structures of all the compounds were confirmed by IR, 1H NMR, 13C NMR and 19F NMR spectroscopy as well as elemental analysis and X-ray crystallography.
- Poorfreidoni, Alireza,Ranjbar-Karimi, Reza,Kia, Reza
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p. 4398 - 4406
(2015/06/16)
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- Preparation and catalytically study of metal-organic frameworks of amine/MIL-53 (Al) as a powerful option in the rapid N-formylation condensation in neat conditions
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This paper reports on the preparation and application of amine/MIL-53 (Al) as highly active catalysts for the N-formylation reaction. These Al-MOFs were found to be an efficient, selective and waste-free green solid catalyst for the net condensation of amines and formic acid. The catalyst can be isolated from the reaction mixture and reused at least 6 times.
- Rostamnia, Sadegh,Karimi, Ziba
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p. 133 - 137
(2015/03/04)
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- Phosphotungstic acid supported on silica-coated CoFe2O4 nanoparticles: An efficient and magnetically-recoverable catalyst for N-formylation of amines under solvent-free conditions
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Phosphotungstic acid (PTA) was rapidly and efficiently anchored on the surface of silica coated cobalt ferrite core to obtain a new three-component CoFe2O4@SiO2-PTA nanocomposite. The resultant composite was characterized by various techniques, including FT-IR, XRD, SEM, EDX, ICP-AES, and VSM. The as-synthesized nanocomposite was examined as catalyst for N-formylation of various amines under solvent-free conditions at room temperature. Due to the presence of magnetic core in this catalyst, it can be easily separated from the reaction media by applying an external magnetic field. The isolated catalyst can be reused for at least five successive times without significant leaching or loss of its high catalytic activity.
- Kooti,Nasiri
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p. 168 - 177
(2015/06/25)
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- Palladium-Catalyzed Synthesis of α-Diimines from Triarylbismuthines and Isocyanides
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In this study, we report a highly selective coupling reaction between triarylbismuthines and isocyanides using palladium diacetate as the catalyst, affording α-diimines, with the formation of three C-C bonds. Among several aryl sources (Ar-YLn: Y = B, Sn, Pb, Sb, Bi, I), only triarylbismuthines successfully undergo coupling with isocyanides to selectively afford α-diimines. The coupling reaction exhibits the advantages of high atom economy and convenient operation, with no need for any additive.
- Kobiki, Yohsuke,Kawaguchi, Shin-Ichi,Ogawa, Akiya
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supporting information
p. 3490 - 3493
(2015/07/28)
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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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- From isonitriles to unsaturated NHC complexes of gold, palladium and platinum
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In a modular template synthesis, unsaturated NHC complexes of gold, palladium and platinum were synthesized from simple metal salts, isonitriles and amines with acetal or ketal groups. Upon the addition of amines with tethered acetal or ketal moieties to the metal-activated isonitrile, first nitrogen acyclic carbene (NAC) complexes are formed. These undergo ring closure and elimination to the unsaturated NHC complexes upon addition of acid. This simple strategy opens an attractive and fast approach to NHC complexes of gold, palladium and platinum. The modular approach allows a fast modification and is well-suited for the synthesis of unsymetrically and symmetrically substituted unsaturated NHC complexes.
- Riedel, Dominic,Wurm, Thomas,Graf, Katharina,Rudolph, Matthias,Rominger, Frank,Hashmi, A. Stephen K.
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supporting information
p. 1515 - 1523
(2015/05/19)
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- Microwave-promoted direct amidation of unactivated esters catalyzed by heteropolyanion-based ionic liquids under solvent-free conditions
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Abstract A simple and efficient procedure for the synthesis of amides directly from unactivated esters and amines catalyzed by heteropolyanion-based ionic liquids under microwave-promoted and solvent-free conditions has been reported. The practical protocol was found to be compatible with different structurally diverse substrates. Moderate to excellent yields, solvent-free media, and operational simplicity are the main highlights. Furthermore, the heteropolyanion-based ionic liquids were easily reusable for this amidation.
- Fu, Renzhong,Yang, Yang,Ma, Yunsheng,Yang, Fei,Li, Jingjing,Chai, Wen,Wang, Quan,Yuan, Rongxin
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p. 4527 - 4531
(2015/06/30)
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- Synthesis, characterization, antibacterial and catalytic activity of a nanopolymer supported copper(ii) complex as a highly active and recyclable catalyst for the formamidation of arylboronic acids under aerobic conditions
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This paper reports on the synthesis and use of a nanopolymer supported copper(ii) complex, as a separable catalyst for the formamidation of arylboronic acids under aerobic conditions. The catalyst was characterized using powder XRD, SEM, EDS, TGA-DTG and FT-IR spectroscopy. This method has the advantages of high yields, elimination of homogeneous catalysts, simple methodology and easy work up. Catalytic efficiency remains unaltered even after several repeated cycles. The synthesized catalyst is found to be more highly toxic towards Gram-positive bacteria than Gram-negative bacteria. This journal is the Partner Organisations 2014.
- Nasrollahzadeh, Mahmoud,Zahraei, Ali,Ehsani, Ali,Khalaj, Mehdi
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p. 20351 - 20357
(2014/06/09)
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- Synthesis and characterization of copper nanoparticles supported on reduced graphene oxide as a highly active and recyclable catalyst for the synthesis of formamides and primary amines
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We report here the synthesis of reduced graphene oxide supported copper nanoparticles (rGO/Cu NPs) from copper (II) sulfate pentahydrate and graphite precursors using a simple protocol. The catalyst was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) and energy dispersive X-ray spectroscopy (EDS). The rGO/Cu NPs is proved to be a useful heterogeneous catalyst in Cu-catalyzed formamidation and amination of arylboronic acids. The catalyst can be recovered by simple filtration from the reaction mixture and reused several times without significant loss of catalytic activity.
- Fakhri, Parisa,Jaleh, Babak,Nasrollahzadeh, Mahmoud
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