Anchoring Ni (II) on Fe3O4@tryptophan: A recyclable,green and extremely efficient magnetic nanocatalyst for one‐pot synthesis of 5‐substituted 1H‐tetrazoles and chemoselective oxidation of sulfides and thiols

A green, novel and extremely efficient nanocatalyst was successfully synthesized by the immobilization of Ni as a transition metal on Fe₃O₄ nanoparticles coated with tryptophan. This nanostructured material was characterized using Fourier transform infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, thermogravimetric analysis, inductively coupled plasma optical emission spectroscopy, vibrating sample magnetometry and X‐ray diffraction. The prepared nanocatalyst was applied for the oxidation of sulfides, oxidative coupling of thiols and synthesis of 5‐substituted 1H‐tetrazoles. The use of non‐toxic, green and inexpensive materials, easy separation of magnetic nanoparticles from a reaction mixture using a magnetic field, efficient and one‐pot synthesis, and high yields of products are the most important advantages of this nanocatalyst.     

A green synthesis of palladium nanoparticles by Sapindus mukorossi seed extract and use in efficient room temperature Suzuki–Miyaura cross‐coupling reaction

A simple and green method for the synthesis of palladium nanoparticles using an aqueous extract of Sapindus mukorossi seed has been demonstrated. The synthesized nanoparticles were characterized using UV–visible spectroscopy, powxder X‐ray diffraction, energy‐dispersive X‐ray analysis and transmission electron microscopy. The nanocatalyst was successfully utilized in an efficient Suzuki–Miyaura cross‐coupling reaction at room temperature.     

Betti base‐modified magnetic nanoparticles as a novel basic nanocatalyst in Knoevenagel condensation and its related palladium nanocatalyst in Suzuki coupling reactions

Betti base‐modified Fe₃O₄ nanoparticles have been successfully designed and synthesized for the first time through the condensation of Fe₃O₄ magnetic nanoparticles coated by (3‐aminopropyl)triethoxysilane with β‐naphthol and benzaldehyde. Their application as a novel magnetic nanocatalyst in the Knoevenagel condensation and also application to immobilization of palladium nanoparticles for Suzuki coupling reactions have been investigated which opens a new field for application of Betti base derivatives in organic transformations. The synthesized inorganic–organic hybrid nanocatalyst has been fully been characterized using Fourier transform infrared, X‐ray diffraction, vibrating sample magnetometry, transmission and scanning electron microscopies, energy‐dispersive X‐ray, wavelength‐dispersive X‐ray and X‐ray photoelectron spectroscopies and inductively coupled plasma techniques. The catalyst was easily separated with the assistance of an external magnet from the reaction mixture and reused for several consecutive runs with no significant loss of its catalytic efficiency. Copyright © 2016 John Wiley & Sons, Ltd.     

One‐pot multicomponent synthesis of novel 2‐(piperazin‐1‐yl) quinoxaline and benzimidazole derivatives,using a novel sulfamic acid functionalized Fe3O4 MNPs as highly effective nanocatalyst

The immobilization of sulfonic acid on the surface of Fe₃O₄ magnetic nanoparticles (MNPs) as a novel acid nanocatalyst has been successfully reported. The morphological features, thermal stability, magnetic properties, and other physicochemical properties of the prepared superparamagnetic core–shell (Fe₃O₄@PFBA–Metformin@SO₃H) were thoroughly characterized using Fourier transform infrared (FTIR), X‐ray diffraction (XRD), energy‐dispersive X‐ray spectroscopy (EDS), field‐emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), thermogravimetric analysis–differential thermal analysis (TGA‐DTA), atomic force microscopy (AFM), dynamic light scattering (DLS), Brunauer–Emmett–Teller (BET), and vibrating sample magnetometer (VSM) techniques. It was applied as an efficient and reusable catalyst for the synthesis of 2‐(piperazin‐1‐yl) quinoxaline and benzimidazole derivatives via a one‐pot multiple‐component cascade reaction under green conditions. The results displayed the excellent catalytic activity of Fe₃O₄@PFBA–metformin@SO₃H as an organic–inorganic hybrid nanocatalyst in condensation and multicomponent Mannich‐type reactions. The easy separation, simple workup, excellent stability, and reusability of the nanocatalyst and quantitative yields of products and short reaction time are some outstanding advantages of this protocol.     

CoFe2O4@SiO2‐CPTES‐Guanidine‐Cu(II): A novel and reusable nanocatalyst for the synthesis of 2,3‐dihydroquinazolin‐4(1H)‐ones and polyhydroquinolines and oxidation of sulfides

CoFe₂O₄@SiO₂‐CPTES‐Guanidine‐Cu(II) magnetic nanoparticles were synthesized and used as a new, inexpensive and efficient heterogeneous catalyst for the synthesis of polyhydroquinolines and 2,3‐dihydroquinazoline‐4(1H)‐ones and for the oxidation of sulfides. The structure of this nanocatalyst was characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, vibrating sample magnetometry, thermogravimetric analysis, X‐ray diffraction and inductively coupled plasma optical emission spectrometry. Simple preparation, high catalytic activity, simple operation, high yields, use of green solvents, easy magnetic separation and reusability of the catalyst are some of the advantages of this protocol.     

Preparation of choline chloride–urea deep eutectic solvent‐modified magnetic nanoparticles for synthesis of various 2‐amino‐4H‐pyran derivatives in water solution

A novel hybrid magnetic nanocatalyst was synthesized by covalent coating of Fe₃O₄ magnetic nanoparticles with choline chloride–urea deep eutectic solvent using 3‐iodopropyltrimethoxysilane as a linker. The structure of this new catalyst was fully characterized via elemental analysis, transmission and scanning electron microscopies, X‐ray diffraction and Fourier transform infrared spectroscopy. It was employed in the synthesis of various 2‐amino‐4H ‐pyran derivatives in water solution via an easy and green procedure. The desired products were obtained in high yields via a three‐component reaction between aromatic aldehyde, enolizable carbonyl and malononitrile at room temperature. The employed nanocatalyst was easily recovered using a magnetic field and reused four times (in subsequent runs) with less than 8% decrease in its catalytic activity.     

Fe3O4‐Methylene diphenyl diisocyanate‐guanidine (Fe3O4–4,4′‐MDI‐Gn): A novel superparamagnetic powerful basic and recyclable nanocatalyst as an efficient heterogeneous catalyst for the Knoevenagel condensation and tandem Knoevenagel‐Michael‐cyclocondensation reactions

In this paper, guanidine groups (Gn) supported on modified magnetic nanoparticles (Fe₃O₄–4,4′‐MDI) were synthesized for the first time. The catalyst synthesized was characterized by various techniques such as SEM (Scanning Electron Microscopy), TEM (Transmission electron microscopy), XRD ( X‐ray Diffraction ), TGA (Thermogravimetric ananlysis), EDS ( Energy‐dispersive X‐ray spectroscopy ) and VSM (vibrating sample magnetometer). The catalyst activity of modified MNPs–MDI‐Gn, as powerful basic nanocatalyst, was probed through the Knoevenagel and Tandem Knoevenagel–Michael‐cyclocondensation reactions. Conversion was high under optimal conditions, and reaction time was remarkably shortened. This nanocatalyst could simply be separated and recovered from the reaction mixture by simple magnetic decantation and reused many times without significant loss of its catalytic activity. Also, the nanocatalyst could be recycled for at least seven (Knoevenagel condensation) and six (Knoevenagel and Tandem Knoevenagel–Michael‐cyclocondensation) additional cycles after they were separated by magnetic decantation and, washed with ethanol, air‐dried, and immediately reused.     

Fe3O4‐supported Schiff‐base copper (II) complex: A valuable heterogeneous nanocatalyst for one‐pot synthesis of new pyrano[2,3‐b]pyridine‐3‐carboxamide derivatives

A novel Cu (II) Schiff‐base complex immobilized on core‐shell magnetic Fe₃O₄ nanoparticles (Fe₃O₄@SPNC) was successfully designed and synthesized. The structural features of these nanoparticles were studied and confirmed by using various techniques including FT‐IR spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy‐dispersive X‐ray spectroscopy (EDS), vibrating sample magnetometer (VSM), X‐Ray diffraction (XRD), wavelength dispersive X‐ray spectroscopy (WDX), and inductively coupled plasma (ICP). These newly synthesized nanoparticles have been used as efficient heterogeneous catalytic system for one‐pot multicomponent synthesis of new pyrano[2,3‐b]pyridine‐3‐carboxamide derivatives. Notably, the catalyst could be easily separated from the reaction mixture by using an external magnet and reused for several successive reaction runs with no significant loss of activity or copper leaching. The present protocol benefits from a hitherto unreported MNPs‐immobilized Cu (II) Schiff‐base complex as an efficient nanocatalyst for the synthesis of newly reported derivatives of pyrano[2,3‐b]pyridine‐3‐carboxamide from one‐pot multicomponent reactions.     

Palladium on magnetic Irish moss: A new nano‐biocatalyst for suzuki type cross‐coupling reactions

A novel heterogeneous magnetic palladium nano‐biocatalyst was designed by utilizing Irish moss, a family of sulfated polysaccharides extracted from algae, as a natural biopolymer. This magnetic Irish moss decorated with palladium (Pd–Fe₃O₄@IM) to form a biomagnetic catalytic system was synthesized and well characterized by FT–IR analysis, X‐ray powder diffraction, field emission scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, atomic absorption spectroscopy and transmission electron microscopy. The catalyst was stable to air and moisture and displayed high catalytic activity in ligand‐free Suzuki–Miyaura cross‐coupling reactions conducted under green chemistry reaction conditions. The aromatic ketones are produced by the cross‐coupling reaction between acid chlorides and aryl boronic acid derivatives in high yields.     

4,5‐Imidazoledicarboxylic acid immobilized on Fe3O4 magnetic nanoparticles: Preparation,characterization, and application as a recyclable and efficient nanocatalyst in the sonochemical condensation reaction

A green synthesis of benzimidazole derivatives using recyclable magnetic 4,5‐imidazoledicarboxylic is described. The magnetic 4,5‐imidazoledicarboxylic (Fe₃O₄@ImDCA) nanocatalyst was characterized completely by infrared spectroscopy (FT‐IR), energy‐dispersive X‐ray spectroscopy (EDX), scanning electron microscopy (SEM), and powder X‐ray diffraction (XRD), and benzimidazoles were characterized by their melting points, FT‐IR, and ¹H NMR. The current approach provides a number of advantages in terms of high yields, low reaction times, the use of green media, and easy work‐up.     

Enantioselective synthesis of 3‐amino‐1‐aryl‐1H‐benzo[f]chromene‐2‐carbonitrile derivatives by Fe3O4@PS‐arginine as an efficient chiral magnetic nanocatalyst

A novel chiral magnetic nanocatalyst was prepared by the surface modification of Fe₃O₄ magnetic nanoparticles (MNPs) with a chloropropylsilane and further by arginine to form Fe₃O₄@propylsilan‐arginine (Fe₃O₄@PS‐Arg). After the structural confirmation of Fe₃O₄@PS‐Arg synthesized MNPs by Fourier transform‐infrared, X‐ray diffraction, field emission‐scanning electron microscopy, transmission electron microscopy, vibrating‐sample magnetometry and thermogravimetric analyses, their catalytic activity was evaluated for one‐pot enantioselective synthesis of 3‐amino‐1‐aryl‐1H‐benzo[f]chromene‐2‐carbonitrile derivatives. The results showed that in the presence of 0.07 g Fe₃O₄@PS‐Arg nanocatalyst and ethanol as solvent, the best reaction yield (96%) was obtained in the least time (5 min). Easy operation, reusability and stability, short reaction time, high reaction yields and good enantioselectivity are the major advantages of the newly synthesized nanocatalyst. Also, this study provides a novel strategy for further research and investigation on the synthesis of new reusable enantioselective catalysts and chiral compounds.     

Design,synthesis, characterization and catalytic performance of a new cellulose‐based magnetic nanocomposite in the one‐pot three‐component synthesis of α‐aminonitriles

A sulfonated magnetic cellulose‐based nanocomposite was prepared and characterized using scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, X‐ray diffraction and Fourier transform infrared spectroscopy. Then, it was used as a green nanocatalyst for the synthesis of α‐aminonitriles by a one‐pot three‐component condensation reaction of aldehydes or ketones, amines and trimethylsilylcyanide in ethanol at room temperature. The reaction procedure is simple, yields are very high, reaction time is very short and the catalyst can be easily separated from the reaction mixture and reused in subsequent reactions without significant loss of catalytic activity. Copyright © 2016 John Wiley & Sons, Ltd.     

Ferrocene‐tagged ionic liquid stabilized on silica‐coated magnetic nanoparticles: Efficient catalyst for the synthesis of 2‐amino‐3‐cyano‐4H‐pyran derivatives under solvent‐free conditions

An advanced novel magnetic ionic liquid based on imidazolium tagged with ferrocene, a supported ionic liquid, is introduced as a recyclable heterogeneous catalyst. Catalytic activity of the novel nanocatalyst was investigated in one‐pot three‐component reactions of various aldehydes, malononitrile and 2‐naphthol for the facile synthesis of 2‐amino‐3‐cyano‐4H‐pyran derivatives under solvent‐free conditions without additional co‐catalyst or additive in air. For this purpose, we firstly synthesized and investigated 1‐(4‐ferrocenylbutyl)‐3‐methylimidazolium acetate, [FcBuMeIm][OAc], as a novel basic ferrocene‐tagged ionic liquid. This ferrocene‐tagged ionic liquid was then linked to silica‐coated nano‐Fe₃O₄ to afford a novel heterogeneous magnetic nanocatalyst, namely [Fe₃O₄@SiO₂@Im‐Fc][OAc]. The synthesized novel catalyst was characterized using ¹H NMR, ¹³C NMR, Fourier transform infrared and energy‐dispersive X‐ray spectroscopies, X‐ray diffraction, and transmission and field emission scanning electron microscopies. Combination of some unique characteristics of ferrocene and the supported ionic liquid developed the catalytic activity in a simple, efficient, green and eco‐friendly protocol. The catalyst could be reused several times without loss of activity.     

Biosynthesis of Pd/MnO2 nanocomposite using Solanum melongena plant extract and its application for the one‐pot synthesis of 5‐substituted 1H‐tetrazoles from aryl halides

In this work, for the first time, Solanum melongena plant extract was used for the green synthesis of Pd/MnO₂ nanocomposite via reduction osf Pd(II) ions to Pd(0) and their immobilization on the surface of manganese dioxide (MnO₂) nanoparticles (NPs) as an effective support. The synthesized nanocomposite were characterized by various analytical techniques such as Fourier transform infrared (FT‐IR), X‐ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), energy dispersive X‐ray spectroscopy (EDS) and UV–Vis spectroscopy. The catalytic activity of Pd/MnO₂ nanocomposite was used as a heterogeneous catalyst for the one‐pot synthesis of 5‐substituted 1H‐tetrazoles from aryl halides containing various electron‐donating or electron‐withdrawing groups in the presence of K ₄ [Fe (CN) ₆ ] as non‐toxic cyanide source and sodium azide. The products were obtained in good yields via a simple methodology and easy work‐up. The nanocatalyst can be recycled and reused several times with no remarkable loss of activity.     

Fe3O4@vitamin B1 as a sustainable superparamagnetic heterogeneous nanocatalyst promoting green synthesis of trisubstituted 1,3‐thiazole derivatives

Fe₃O₄@vitamin B₁ was designed and prepared as an inexpensive and efficient heterogeneous nanocatalyst for the synthesis of new 1,3‐thiazol derivatives. The structure of the nanomagnetic catalyst was comprehensively characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, energy‐dispersive X‐ray spectroscopy, vibrating sample magnetometry and thermogravimetric analysis. The three‐component, one‐pot condensation of arylglyoxal monohydrate, cyclic 1,3‐dicarbonyls and thioamides in water as a green solvent was applied for the preparation of 1,3‐thiazol derivatives. Simple preparation of the catalyst from commercially available materials, high catalytic activity, simple operation, short reaction times, high yields and use of green solvent are some advantages of this protocol. The superparamagnetic nanocatalyst is magnetically separable and retains its stability after recycling for at least five consecutive runs without detectable activity loss.     

CuI/Fe3O4 NPs@Biimidazole IL‐KCC‐1 as a leach proof nanocatalyst for the synthesis of imidazo[1,2‐a]pyridines in aqueous medium

In the present work, an innovative leach proof nanocatalyst based on dendritic fibrous nanosilica (DFNS) modified with ionic liquid loaded Fe₃O₄ NPs and CuI salts was designed and applied for the rapid synthesis of imidazo[1,2‐a]pyridines from the reaction of phenyl acetylene, 2‐aminopyridine, and aldehydes in aqueous medium. The structure of the synthesized nanocatalyst was studied by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), Fourier transform infrared (FT‐IR), flame atomic absorption spectroscopy (FAAS), energy‐dispersive X‐ray (EDX), and X‐ray diffraction (XRD), vapor–liquid–solid (VLS), and adsorption/desorption analysis (Brunauer–Emmett–Teller [BET] equation) instrumental techniques. CuI/Fe₃O₄NPs@IL‐KCC‐1 with high surface area (225 m² g^?1) and porous structure not only exhibited excellent catalytic activity in aqueous media but also, with its good stability, simply recovered by an external magnet and recycled for eight cycles without significant loss in its intrinsic activity. Higher catalytic activity of CuI/Fe₃O₄NPs@IL‐KCC‐1 is due to exceptional dendritic fibrous structure of KCC‐1 and the ionic liquid groups that perform as strong anchors to the loaded magnetic nanoparticles (MNPs) and avoid leaching them from the pore of the nanocatalyst. Green reaction media, shorter reaction times, higher yields (71–97%), easy workup, and no need to use the chromatographic column are the advantages of the reported synthetic method.     

N‐(3‐silyl propyl) diethylene triamine N,N',N'‐tri‐sulfonic acid immobilized on Fe3‐xTixO4 magnetic nanoparticles: A new recyclable heterogeneous nanocatalyst for the synthesis of hexahydroquinolines

In the present study, for the first time N‐(3‐silyl propyl) diethylene triamine N,N',N''‐tri‐sulfonic acid (SPDETATSA) was grafted on magnetic Fe_3‐xTi_xO₄ nanoparticles. The structure of the resulted nanoparticles was characterized based on Fourier‐transform infrared (FT‐IR), energy‐dispersive X‐ray spectroscopy (EDX), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA), and vibrating sample magnetometer (VSM) analyses. The results confirmed the successful immobilization of sulfamic acid groups onto the magnetic support. These nanoparticles exhibited high catalytic activity as novel magnetically recyclable acid nanocatalyst in the synthesis of a diverse range of hexahydroquinolines through one‐pot tandem reactions in excellent yields. Also, this nanocatalyst performed satisfactory catalytic maintenance of activity for the synthesis of the reaction products after 4 rounds of recycling with no considerable loss of activity.     

Solvent‐free synthesis of propargylamines catalyzed by an efficient recyclable ZnO‐supported CuO/Al2O3 nanocatalyst

An efficient nanocatalyst of ZnO‐supported CuO/Al₂O₃ (CuO/ZnO/Al₂O₃ nanocatalyst) was prepared by the co‐precipitation method and characterized by scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, X‐ray powder diffraction and Brunauer–Emmett–Teller surface area analysis. CuO/ZnO/Al₂O₃ nanocatalyst proved to be a very efficient catalyst on the synthesis of propargylamines under solvent‐free conditions in high yields. Moreover, the catalyst can be recyclable without reducing catalytic activity up to five times.     

Microwave‐Assisted Synthesis of a Superparamagnetic Surface‐Functionalized Porous Fe3O4/C Nanocomposite

An Fe₃O₄/C nanocomposite was synthesized in a microwave‐assisted hydrothermal reaction. This green wet‐chemical approach is simple, low‐cost, and ideal for large‐scale production. The resulting composite material was characterized by transmission electron microscopy, powder X‐ray diffraction, energy‐dispersive X‐ray spectroscopy, Brunauer–Emmett–Teller analysis, X‐ray photoelectron spectroscopy, vibrating sample magnetometry, and UV/Vis spectroscopy. The product possesses porous structures and exhibits superparamagnetic behavior. Interestingly, its functional groups were inherited from the starting materials. This hydrophilic and biocompatible nanocomposite may find applications in catalysis, separation, adsorption, and bionanotechnology.     

Magnetic nanoporous MCM‐41 supported ionic liquid/palladium complex: An efficient nanocatalyst with high recoverability

In this study, a novel magnetic mesoporous MCM‐41 silica supported ionic liquid/palladium complex (Fe₃O₄@MCM@IL/Pd) with core‐structure was prepared and characterized and its catalytic performance was developed under green conditions. The Fe₃O₄@MCM@IL/Pd was prepared via a post grafting method and was characterized using Fourier transform infrared spectroscopy, thermal gravimetric analysis, wide‐ and low‐angle powder X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, vibration sample magnetometer and energy‐dispersive X‐ray analyses. This was applied as an efficient and recoverable nanocatalyst for the one‐pot synthesis of pyrano[2,3‐d]pyrimidine derivatives under ultrasonic conditions. The catalyst was magnetically recovered and reused for 12 consecutive cycles without significant loss of its activity and selectivity.