Fe3O4@SiO2–ZrCl2‐MNPs: A novel magnetic catalyst for the clean and efficient cascade synthesis of 1‐(benzothiazolylamino)methyl‐2‐naphthol derivatives in the absence of solvent

A green, simple and eco‐friendly three‐component condensation for the synthesis of 1‐(benzothiazolylamino)methyl‐2‐naphthols using new magnetic nanoparticles formulated as Fe₃O₄@SiO₂–ZrCl₂‐MNPs is described. Considering the economic and environmental aspects, the method provides some advantages such as clean procedure, solvent‐free conditions, simple operation and work‐up, relatively short reaction times and high yields of the products. Moreover the introduced catalyst can be readily recovered up to 4 consecutive runs with consistent activity using an external magnet.     

CuBr‐catalysed one‐pot multicomponent synthesis of 3‐substituted 2‐thioxo‐2,3‐dihydroquinazolin‐4(1H)‐one derivatives

A novel methodology is presented for the synthesis of 3‐substituted 2‐thioxo‐2,3‐dihydroquinazolin‐4(1H)‐one derivatives based on an efficient tandem multicomponent reaction using copper bromide as catalyst. This methodology is based on the multicomponent one‐pot reaction of methyl 2‐bromobenzoate, phenylisothiocyanate derivatives and sodium azide in the presence of copper bromide and l ‐proline under basic conditions. To show the generality of the method, various phenylisothiocyanates bearing electron‐donating or electron‐withdrawing functionalities were used and the desired products were obtained in high isolated yields.     

Sulfamic acid immobilized on amino‐functionalized magnetic nanoparticles: A new and active magnetically recoverable catalyst for the synthesis of N‐heterocyclic compounds

Sulfamic acid immobilized on amino‐functionalized magnetic nanoparticles (MNPs/DETA‐SA) was successfully fabricated and characterized using various techniques. Diameters of approximately 15 nm for the MNPs/DETA‐SA were observed from scanning electron microscopy images. The as‐fabricated nanocomposite was applied as an efficient and magnetically reusable catalyst for the synthesis of 2,3‐dihydroquinazoline‐4(1H)‐one and polyhydroquinoline derivatives. All products were obtained in good to excellent yields. Recovery tests confirm that the catalyst can be readily recovered using an external magnet and reused many times without significant loss of its catalytic activity.     

Synthesis and characterization of bromine source supported on magnetic Fe3O4 nanoparticles: A new,versatile and efficient magnetically separable catalyst for organic synthesis

Tribenzylammonium tribromide supported onto magnetic nanoparticles (Br₃‐TBA‐Fe₃O₄) as a bromine source was successfully synthesized and characterized using Fourier transform infrared spectroscopy, thermogravimetric analysis, X‐ray diffraction, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy and vibrating sample magnetometry. The synthesized catalyst is shown to be a versatile and highly efficient heterogeneous catalyst for the Knoevenagel condensation and synthesis of 2,3‐dihydroquinazolin‐4(1H )‐one and polyhydroquinoline derivatives. To the best of the authors' knowledge, this is the first report of the use of a bromine source immobilized on Fe₃O₄ nanoparticles as a magnetically separable catalyst for these reactions. The nanosolid catalyst can be magnetically recovered and reused readily several times without significant loss in catalytic efficiency.     

One‐pot synthesis of 1‐ and 5‐substituted 1H‐tetrazoles using 1,4‐dihydroxyanthraquinone–copper(II) supported on superparamagnetic Fe3O4@SiO2 magnetic porous nanospheres as a recyclable catalyst

An effective one‐pot, convenient process for the synthesis of 1‐ and 5‐substituted 1H‐tetrazoles from nitriles and amines is described using1,4‐dihydroxyanthraquinone–copper(II) supported on Fe₃O₄@SiO₂ magnetic porous nanospheres as a novel recyclable catalyst. The application of this catalyst allows the synthesis of a variety of tetrazoles in good to excellent yields. The preparation of the magnetic nanocatalyst with core–shell structure is presented by using nano‐Fe₃O₄ as the core, tetraethoxysilane as the silica source and poly(vinyl alcohol) as the surfactant, and then Fe₃O₄@SiO₂ was coated with 1,4‐dihydroxyanthraquinone–copper(II) nanoparticles. The new catalyst was characterized using Fourier transform infrared spectroscopy, X‐ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, dynamic light scattering, thermogravimetric analysis, vibration sample magnetometry, X‐ray photoelectron spectroscopy, nitrogen adsorption–desorption isotherm analysis and inductively coupled plasma analysis. This new procedure offers several advantages such as short reaction times, excellent yields, operational simplicity, practicability and applicability to various substrates and absence of any tedious workup or purification. In addition, the excellent catalytic performance, thermal stability and separation of the catalyst make it a good heterogeneous system and a useful alternative to other heterogeneous catalysts. Also, the catalyst could be magnetically separated and reused six times without significant loss of catalytic activity. Copyright © 2016 John Wiley & Sons, Ltd.     

A silicon‐assisted synthesis of (E)‐β‐haloenamides from N‐vinylamides

(E)‐β‐Iodoenamides and (E)‐β‐iodoenimides can be easily obtained from N‐vinyl derivatives (N‐vinylamides and N‐vinylimides) by stereoselective ruthenium‐catalysed silylative coupling with vinyltrimethylsilane (Marciniec coupling) and subsequent stereospecific silicon–iodine exchange. Bromodesilylation of (E)‐β‐silylenimides affords (E)‐β‐bromoenimides, while the analogous reactions involving (E)‐β‐silylenamides lead to decomposition of substrates. N‐Halosuccinimides have been found as the most effective halogenating agents in the desilylation step under mild conditions. The ruthenium‐catalysed silylation/halodesilylation sequence can be performed in a one‐pot procedure. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and characterization of copper(II) Schiff base complex supported on Fe3O4 magnetic nanoparticles: a recyclable catalyst for the one‐pot synthesis of 2,3‐dihydroquinazolin‐4(1H)‐ones

Fe₃O₄–Schiff base of Cu(II) is found to be a recyclable and heterogeneous catalyst for the rapid and efficient synthesis of various 2,3‐dihydroquinazolin‐4(1H)‐one derivatives from the two‐component condensation of 2‐aminobenzamide and an aldehyde. This reaction is simple, green and cost‐effective. Separation and recycling can also be easily done by magnetic decantation of the Fe₃O₄ nanoparticles with an external magnet. The prepared catalyst was characterized using thermogravimetry, Fourier transform infrared spectroscopy, vibrating sample magnetometry, inductively coupled plasma analysis, X‐ray diffraction and scanning electron microscopy. Copyright © 2015 John Wiley & Sons, Ltd.     

Supramolecular Fe3O4@PEG/−diaza crown ether@Ni: a novel magnetically reusable nano catalyst for the clean synthesis of 2‐aryl‐2,3‐dihydroquinazolin‐4(1H)‐ones

Ni@diaza crown ether complex supported on magnetic nanoparticle was provided by grafting technique. The catalytic activity of Fe₃O₄@diaza crown ether@Ni was explored through one‐pot synthesis of 2,3‐dihydroquinazolin‐4(1H)‐ones and it was used as an efficient and recoverably constant nanocatalyst. FT‐IR, SEM, TEM, XRD, BET, ICP, EDS, and TGA techniques were employed to specify the nanocatalyst. This heterogeneous catalyst demonstrated acceptable recyclability and could be used again several times with no considerable loss of its catalytic activity.     

Fe3O4@silica‐MCM‐41@DABCO: A novel magnetically reusable nanostructured catalyst for clean in situ synthesis of substituted 2‐aminodihydropyrano[3,2‐b]pyran‐3‐cyano

DABCO (1,4‐diazabicyclo[2.2.2]octane)‐modified magnetite with silica‐MCM‐41 shell (Fe₃O₄@silica‐MCM‐41@DABCO) as an effective, magnetic and novel heterogeneous reusable nanocatalyst was synthesized and analysed using various techniques. Evaluation of the catalytic activity of this nanocatalyst was performed in the clean synthesis of substituted 2‐aminodihydropyrano[3,2‐b]pyran‐3‐cyano in high yields via in situ reaction of azido kojic acid, malononitrile and various aldehydes.     

Dendrimer‐encapsulated Cu(Π) nanoparticles immobilized on superparamagnetic Fe3O4@SiO2 nanoparticles as a novel recyclable catalyst for N‐arylation of nitrogen heterocycles and green synthesis of 5‐substituted 1H‐tetrazoles

In this study, dendrimer‐encapsulated Cu(Π) nanoparticles immobilized on superparamagnetic Fe₃O₄@SiO₂ nanoparticles were prepared via a multistep‐synthesis. Then, the synthesized composite was fully characterized by various techniques such as fourier transform infrared (FT‐IR) spectroscopy, X‐ray diffraction (XRD), dynamic light scattering (DLS), UV‐vis spectroscopy, energy dispersive X‐ray analysis (EDX), thermogravimetric analysis (TGA) and vibration sample magnetometer (VSM). From the information gained by FE‐SEM and TEM studies it can be inferred that the particles are mostly spherical in shape and have an average size of 50 nm. Also, the amount of Cu is determined to be 0.51 mmol/g in the catalyst by inductively coupled plasma (ICP) analyzer. This magnetic nano‐compound has been successfully applied as a highly efficient, magnetically recoverable and stable catalyst for N‐arylation of nitrogen heterocycles with aryl halides (I, Br) and arylboronic acids without using external ligands or additives. The catalyst was also employed in a one‐pot, three‐component reaction for the efficient and green synthesis of 5‐substituted 1H‐tetrazoles using various aldehydes, hydroxylamine hydrochloride and sodium azide in water. The magnetic catalyst can be easily separated by an external magnet bar and is recycled seven times without significant loss of its activity.     

Fe3O4 nanoparticles: A powerful and magnetically recoverable catalyst for the synthesis of novel calix[4]resorcinarenes

A simple synthesis of novel and known calix[4]resorcinarenes derivatives has been achieved by the condensation of resorcinol and different aromatic aldehydes in the presence of catalytic amounts of Fe₃O₄ nanoparticles under solvent-free conditions.The experimental conditions have been thoroughly optimized and established,allowing significant rate enhancements and good to excellent yields.The reactions can be run safely without using any toxic organic solvents under mild reaction conditions.The Fe₃O₄ nanoparticles were characterized by powdered X-ray diffraction（XRD）,transmission electron microscopy（TEM） and FT-IR spectroscopy.     

CoFe2O4/TMU‐17‐NH2 as a hybrid magnetic nanocomposite catalyst for multicomponent synthesis of dihydropyrimidines

A new magnetic metal–organic framework nanocomposite (CoFe₂O₄/TMU‐17‐NH₂) was prepared via an embedding approach by synthesis of the metal–organic framework crystals in the presence of magnetic cobalt ferrite nanoparticles. We demonstrated that the resulting magnetic nanocomposite can serve as a recyclable nanocatalyst for one‐pot synthesis of bis‐3,4‐dihydropyrimidin‐2(1H)‐one and 3,4‐dihydropyrimidin‐2(1H)‐one derivatives via three‐component reaction of 1,3‐diketone, urea or thiourea and aromatic aldehyde under solvent‐free conditions. CoFe₂O₄/TMU‐17‐NH₂ was characterized using various techniques. The recovery of the nanocomposite was achieved by a simple magnetic decantation and it was reused at least seven times without significant degradation in catalytic activity.     

Novel ionic liquid supported on Fe3O4 nanoparticles as an efficient catalyst for the synthesis of new chromenes

An efficient procedure for the synthesis of new chromenes by the multicomponent reaction of aldehydes, 4‐hydroxycoumarin and 2‐hydroxynaphthalene‐1,4‐dione in the presence of an ionic liquid supported on Fe₃O₄ nanoparticles is described. The ionic liquid supported on Fe₃O₄ nanoparticles as a magnetic catalyst gives products in high yields. Significant features of this method are: short reaction times, excellent yields, green method and use of an effective catalyst that can be recovered and reused many times without loss of its catalytic activity.     

A One‐Pot O‐Phosphinative Passerini/Pudovik Reaction: Efficient Synthesis of Highly Functionalized α‐(Phosphinyloxy)amide Derivatives

A one‐pot O‐phosphinative Passerini/Pudovik reaction has been developed, based on reacting aldehydes, isocyanides, and phosphinic acids followed by the addition of second aldehydes to form the corresponding α‐(phosphinyloxy)amide derivatives. This is the first reported instance of a Passerini‐type, isocyanide‐based multicomponent reaction using a phosphinic acid instead of a carboxylic acid. The nucleophilicity of the phosphinate group allows a subsequent catalytic Pudovik‐type reaction, affording the highly functionalized α‐(phosphinyloxy)amide derivative in high yield. A wide range of aldehydes and isocyanides are applicable to this reaction.     

One‐pot solvent‐free synthesis of novel functionalized ethyl 2‐(alkylimino)‐4‐methyl‐3‐(alkanoyl)‐2,3‐dihydrothiazole‐5‐carboxylates

A green and efficient one‐pot two‐step synthesis of ethyl 2‐(alkylimino)‐4‐methyl‐3‐(alkanoyl)‐2,3‐dihydrothiazole‐5‐carboxylates from the reaction between acyl chlorides, ammonium thiocyanate, primary alkylamines, and ethyl 2‐chloroacetoacetae under mild, solvent‐ and catalyst‐free conditions at room temperature is presented. This efficient and straightforward technique gave the expected products in good to high yields in 2–4 hr without the creation of any by‐product in all reactions.     

Polypyrrole/Fe3O4/CNT as a recyclable and highly efficient catalyst for one‐pot three‐component synthesis of pyran derivatives

Polypyrrole (PPY)/Fe₃O₄/CNT has been synthesized and characterized by FT‐IR, TEM and SEM techniques and its catalytic activity has been evaluated in the synthesis of several series of pyran derivatives. Tetrahydrobenzo[b]pyranes, 4H‐pyran‐3‐carboxylates, 4H,5H‐pyrano[3,2‐c]chromenes and dihydropyrano[2,3‐c]pyrazoles have been successfully prepared from one‐pot three‐component condensation of aldehyde, malononitrile and active methylene‐containing compounds (dimedone /ethyl acetoacetate/4‐hydroxycoumarin/3‐methyl‐2‐pyrazoline‐5‐one) using PPY/Fe₃O₄/CNT as a new and reusable heterogeneous catalyst. The present method offer several advantages such as; high yields of products, short reaction times, easy work‐up procedure and easy separation of the catalyst from the reaction mixture due to its magnetic character. Furthermore, chemoselective synthesis of bis‐benzo[b]pyran from terephthalaldehyde can be achieved by this method.     

Copper Schiff base complex immobilized on silica‐coated Fe3O4 nanoparticles: a recoverable and efficient catalyst for synthesis of polysubstituted pyrroles

In this work, a copper Schiff base complex immobilized on silica‐coated Fe₃O₄ nanoparticles is synthesized, and studied as a highly efficient, recyclable, green and heterogeneous catalyst for the preparation of polysubstituted pyrroles under solvent‐free and mild conditions. This new catalyst was characterized by different techniques, such as Fourier transform infrared (FT‐IR), X‐ray powder diffraction (XRD), field‐emission scanning electron microscopy (SEM), energy‐dispersive X‐ray spectroscopy (EDX), inductively coupled plasma (ICP) and vibrating sample magnetometry (VSM). The simple and environmentally one‐pot multicomponent condensation of nitromethane, an aryl aldehyde, a 1,3‐dicarbonyl compound and an amine in the presence of above catalyst affords the title compounds at room temperature. At the end, we compared the results for the synthesis of polysubstituted pyrroles in the presence of our nanocatalyst with previously reported catalysts in the literature.     

Synthesis and characterization of sodium polyaspartate‐functionalized silica‐coated magnetite nanoparticles: A heterogeneous,reusable and magnetically separable catalyst for the solvent‐free synthesis of 2‐amino‐4H‐chromene derivatives

An efficient and facile method was used for the synthesis of sodium polyaspartate‐functionalized silica‐coated magnetite nanoparticles. The structure of this nanoparticle was characterized by scanning electron microscopies, X‐ray diffraction, energy‐dispersive X‐ray, Fourier transform infrared spectroscopies and vibrating sample magnetometry. Then, this compound was used as a reusable heterogeneous catalyst for green synthesis of 2‐amino‐4H‐chromene derivatives via one‐pot three‐component reactions. This novel material showed great catalytic performance and the reactions which were carried out by this catalyst showed good to excellent yields. Besides, the catalyst could easily be separated from the reaction mixture by using an external magnetic field and it was stable enough to reuse several times without any significant reduction in the yield of reactions. Eco‐friendliness, high purity of the desired products, short reaction time and easy workup procedure can be mentioned as the other advantages of this method.     

l‐Proline‐functionalized Fe3O4 nanoparticles as a novel magnetic chiral catalyst for the direct asymmetric Mannich reaction

l ‐Proline has been successfully anchored on the surface of magnetic nanoparticles and characterized using powder X‐ray diffraction, scanning electron microscopy, vibrating sample magnetometry and Fourier transform infrared spectroscopy. These nanoparticles as a chiral catalyst have been employed to promote the direct asymmetric Mannich reaction. The corresponding products are obtained in high yields with high level of diastereoselectivity (up to 99:1 dr) in the presence of Fe₃O₄– l ‐proline. Also this heterogeneous catalyst can be recovered easily and reused many times without significant loss of its catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis of Functionalized 1‐Benzamido‐1,4‐dihydropyridines via a One‐Pot Two‐Step Four‐Component Reaction

The one‐pot four‐component reaction of benzohydrazide, acetylenedicarboxylate, aromatic aldehydes and malononitrile in ethanol with triethylamine as base catalyst afforded functionalized 1‐benzamido‐1,4‐dihydropyridines in satisfactory yields. Under similar conditions, picolinohydrazide or nicotinohydrazide can also be successfully utilized in the reactions to give corresponding functionalized 1,4‐dihydropyridines. ¹H NMR data indicated that an equilibrium of cis/trans‐conformations exist in 1‐benzamido‐1,4‐dihydropyridines.