Manganese(III) porphyrin anchored onto multiwall carbon nanotubes: An efficient and reusable catalyst for the heterogeneous reduction of aldehydes and ketones

Reduction of a variety of carbonyl compounds with NaBH₄, using Mn-porphyrin, meso-tetrakis(4-hydroxyphenyl)porphyrinatomanganese(III), supported onto functionalized multiwall carbon nanotubes has been investigated. The heterogeneous catalyst was characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV–vis spectroscopy. The amount of catalyst loading on the nanotubes was determined by atomic absorption spectroscopy. Thermogravimetric analysis (TGA) demonstrated that the nanocatalyst was thermally stable to almost 300 °C, exhibiting high thermostability of the catalyst over a broad range of temperatures. This heterogeneous catalyst proved to be an efficient catalyst in the aerobic reduction of various aldehydes and ketones with NaBH₄. In the presence of the nanocatalyst, NaBH₄ can readily reduce a variety of aldehydes in good to excellent yields (50–100%) and ketones in excellent yields (100%) to their corresponding alcohols. The separation of the catalyst is very simple and economic. Also, FTIR spectra after four successive cycles showed that the catalyst was strongly anchored to the nanotubes.     

HAp‐encapsulated γ‐Fe2O3‐supported dual acidic heterogeneous catalyst for highly efficient one‐pot synthesis of benzoxanthenones and 3‐pyranylindoles

A novel method is reported for the synthesis of benzoxanthenone and 3‐pyranylindole derivatives via one‐pot three‐component reactions using a newly synthesized HAp‐encapsulated γ‐Fe₂O₃‐supported dual acidic heterogeneous catalyst, as a reusable and highly efficient nanocatalyst. In this protocol the use of the nanocatalyst provided a green, useful and rapid method to generate products in short reaction times (4–20 min) and in excellent yields (87–96%). The paramagnetic nature of the catalyst provided a simple, trouble‐free and facile approach for the separation of the catalyst by applying an external magnet, and it could be used in eight cycles without significant loss in catalytic efficiency.     

L-Tyrosine-Pd complex supported on Fe3O4 magnetic nanoparticles: A new catalyst for C–C coupling and Synthesis of sulfides

In the present work, Fe₃O₄@L-Tyrosine-Pd heterogeneous nanocatalyst was prepared by a simple and inexpensive procedure. The prepared nanocatalyst was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray Diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), inductively coupled plasma optical emission spectroscopy (ICP-OES), scanning electron microscopy (SEM), Transmission electron microscopy)TEM(, X-ray mapping, thermal gravimetric analysis (TGA), N₂ adsorption and desorption (BET) and vibrating sample magnetometer (VSM) techniques. Besides, it was employed as an efficent catalyst for C-C cross coupling and S-arylation reactions under green conditions. The optimized conditions for these reactions are described. The heterogeneous catalyst can be easily separated by applying a simple magnet and can also be reused in several consecutive runs without appreciable change in its catalytic activity.     

Cu(I)-anchored polyvinyl alcohol coated-magnetic nanoparticles as heterogeneous nanocatalyst in Ullmann-type C–N coupling reactions

In this paper, the preparation of a novel magnetic nanocatalyst (Fe₃O₄@PVA/CuCl) is described, which involves coating of polyvinyl alcohol (PVA) onto the surface of Fe₃O₄ nanoparticles and its subsequent coordination with CuCl catalyst. The nanocatalyst was characterized by various analytical methods, including Fourier-transform infrared, X-ray diffraction, inductively coupled plasma spectroscopy, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy, vibrating-sample magnetometry, and EDX elemental mapping. Moreover, the nanocatalyst was efficiently used in the N-arylation of amines via the formation of a carbon–nitrogen bond between the aryl halides and amines by Ullmann-type coupling reactions. The catalyst was sufficiently stable and can be reused for at least seven times in a model Ullmann reaction without remarkable alteration in its catalytic behavior. Heterogeneity of the catalyst was investigated by a hot filtration test.     

Preparation of a trihydrazinotriazine-functionalized core-shell nanocatalyst as an extremely efficient catalyst for the synthesis of benzoxanthenes

In recent years, there is a high demand on utilizing heterogeneous nanocatalysts in organic synthetic routes because of their green approach, facile purification of the products, and reusability of the catalyst. Herein, we introduced trihydrazinotriazine (THDT)-coated Fe₃O₄@SiO₂ as a novel amino-functionalized magnetic nanocompostie. We fully characterized the nanocatalyst and proved the morphology and magnetic property of the nanoparticles by using essential analyses. The basic attribute of the amino-rich porous surface of the nanocomposite provides a desirable environment for enhancing various reaction conditions. To examine the applicability of the nanocatalyst in organic reactions, we synthesized several benzoxanthenes using Fe₃O₄@SiO₂-THDT nanocatalysts. The nanocomposite successfully improved the reaction conditions and provided the benzoxanthenes in an environmentally friendly procedure, which afforded product in excellent yields (80–96%) and reduced time. The nanomagnetic catalyst was easily recovered after each trial by using an external magnet. After six successive runs, the loss of catalytic activity of the nanocomposite was negligible. Finally, we propounded a plausible mechanism for the preparation of the benzoxanthenes derivatives using the THDT-functionalized core-shell magnetic nanocatalyst.     

Trisaminomethane–cobalt complex supported on Fe3O4 magnetic nanoparticles as an efficient recoverable nanocatalyst for oxidation of sulfides and C–S coupling reactions

In this work, trisaminomethane–cobalt complex immobilized onto the surface of Fe₃O₄ magnetic nanoparticles was successfully prepared via a simple and inexpensive procedure. The prepared nanocatalyst was considered a robust and clean nanoreactor catalyst for the oxidation and synthesis of sulfides under green conditions. This ecofriendly heterogeneous catalyst was characterized by Fourier transform infrared spectroscopy, X-ray diffractometry, energy-dispersive X-ray spectroscopy, inductively coupled plasma-atomic emission spectroscopy, thermogravimetric analysis, vibrating sample magnetometry, X-ray mapping, scanning electron microscopy, and transmission electron microscopy techniques. Use of green medium, easy separation and workup, excellent reusability of the nanocatalyst, and short reaction time are some outstanding advantages of this method.     

Functionalized CoFe2O4/lamellar mesopore silica anchored to melamine nanocomposite as a novel catalyst for synthesis of 4H-chromenes under mild conditions

In this research, it was displayed an efficient method for the one-pot reaction of cyclohexanone, benzaldehyde and malononitrile for the synthesis of 4H-chromenes by using CoFe₂O₄/lamellar mesopore silica anchored to melamine as a magnetic nanocatalyst. This nanocatalyst was prepared in several steps and discriminated by XRD, FT-IR, SEM, VSM, TGA and BET techniques. The catalyst has a large active base site that has functionalized in both the surface and the pore of nanostructure. The advantages of magnetic nanocatalyst were simple accessible, heterogeneous nanocatalyst, easy work up and reusability. The various derivatives of 4H-chromenes were synthesized in the presence of CoFe₂O₄/lamellar mesopore silica/melamine magnetic nanocatalyst with the excellent yields and appropriate times. The products were identified by the melting point, FT-IR, ¹H NMR, ¹³C NMR and C.H.N techniques.     

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.     

Synthesis,characterization, and catalytic activity of supported molybdenum Schiff base complex as a magnetically recoverable nanocatalyst in epoxidation reaction

A heterogeneous nanocatalyst was prepared via covalent anchoring of dioxomolybdenum(VI) Schiff base complex on core–shell structured Fe₃O₄@SiO₂. The properties and the nature of the surface-fixed complex have been identified by a series of characterization techniques such as SEM, EDX, XRD, TGA, FT-IR, and VSM. The synthesized hybrid material was an efficient nanocatalyst for selective oxidation of olefins to corresponding epoxides with t-BuOOH in high yields and selectivity. The catalyst could be conveniently recovered by applying an external magnetic field and reused several times without significant loss of efficiency.     

ZnFe2O4 nanoparticles: A green and recyclable magnetic catalyst for fast and regioselective conversion of epoxides to vicinal hydroxythiocyanates using NH4SCN under solvent-free conditions

ZnFe₂O₄ nanoparticles were synthesized and used as recyclable magnetic catalyst in the solvent-free conversion of different epoxides to vicinal hydroxythiocyanates with NH₄SCN at room temperature. The reactions were carried out by grinding in a mortar with perfect regioselectivity within short times (2-25 min) and with high to excellent yields (75–95%). The nanocatalyst was separated easily using an external magnet and reused for four consecutive cycles without any noticeable loss of efficiency or magnetic property.     

Silica iminopyridine-functionalized nanomaghemite enhances the oxygenation activity and durability of simple Co(II) salophen complex

A novel magnetically recoverable catalyst was produced by coordinative attachment of Co(II) salophen complex to silica iminopyridine (SIPy)-functionalized-γ-Fe₂O₃ magnetic nanoparticles (SMNP@SIPy/Co(II) salophen). The vibration spectra and compositional data provided sufficient evidences for the structural integrity of as-prepared organic–inorganic nanohybrid. The magnetic nanocatalyst proved to be an efficient and selective heterogeneous catalyst for oxidation of different benzylic alcohols and featured higher catalytic activity and stability than that of homogenous counterpart. A TOF of 151 h⁻¹ and TON of more than 322 were obtained for oxidation of 4-cholrobenzyl alcohol in this catalytic system. The supported catalyst could easily be recovered from the reaction mixture by an external magnetic field and reused for subsequent experiments with consistent catalytic activity.     

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.     

Immobilization of copper nanoparticles on WO3 with enhanced catalytic activity for the synthesis of 1,2,3-triazoles

In this study, a heterogeneous catalyst based on copper nanoparticles immobilized on metal oxide, WO₃, was fabricated using an impregnation method as an easy and straightforward nanoparticle synthesis strategy. The successful synthesis of the nanocatalyst was confirmed using various spectroscopic techniques such as X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis, and transmission electron microscopy. The catalytic performance of the well-characterized material was evaluated through the azide–alkyne cycloaddition reaction (click reaction) in the aqueous medium. To optimize reaction conditions, different reaction parameters such as nanocatalyst amount, reaction time, temperature, and solvents were studied. Experimental results showed that as-prepared nanocatalyst (Cu/WO₃) could act as an effective and reusable heterogeneous catalyst in water for the synthesis of 1,2,3-triazoles in good-to-excellent yields. In addition, Cu/WO₃ has some advantages such as simple preparation procedure, easy separation, and recyclability for three runs with no remarkable loss of catalytic activity, which is essential from a catalytic application point of view.     

Synthesis and application of novel 1,2,3‐triazolylferrocene‐containing ionic liquid supported on Fe3O4 nanocatalyst in the synthesis of new pyran‐substituted Betti bases

A novel magnetic ferrocene‐labelled ionic liquid based on triazolium, [Fe₃O₄@SiO₂@Triazol‐Fc][HCO₃], has been synthesized and has been successfully introduced as a recyclable heterogeneous nanocatalyst. The catalytic activity of the novel magnetic nanoparticles was evaluated in the one‐pot three‐component synthesis of a wide variety of Betti bases. A simple, facile and highly efficient green method has been developed for the synthesis of kojic acid‐containing Betti base derivatives at room temperature. Additionally, this new protocol has notable advantages such as short reaction times, green reaction conditions, high yields and simple workup and purification steps. Also, the novel nanocatalyst could be easily recovered using an external magnetic field and reused for six consecutive reaction cycles without significant loss of activity. The newly synthesized nanocatalyst was characterized using Fourier transform infrared spectroscopy, X‐ray diffraction, energy‐dispersive X‐ray spectroscopy, field emission scanning electron microscopy, transmission electron microscopy and Brunauer–Emmett–Teller measurements.     

Hiyama cross‐coupling reaction using Pd(II) nanocatalyst immobilized on the surface of Fe3O4@SiO2

We report a simple process for the synthesis of Fe₃O₄@SiO₂/APTMS (APTMS = 3‐aminopropyltrimethoxysilane) core–shell nanocatalyst support. The new nanocatalyst was prepared by stabilization of Pd(cdha)₂ (cdha = bis(2‐chloro‐3,4‐dihydroxyacetophenone)) on the surface of the Fe₃O₄@SiO₂/APTMS support. The structure and composition of this catalyst were characterized using various techniques. An efficient method was developed for the synthesis of a wide variety of biaryl compounds via fluoride‐free Hiyama cross‐coupling reactions of aryl halides with arylsiloxane, with Fe₃O₄@SiO₂/APTMS/Pd(cdha)₂ as the catalyst under reaction conditions. This methodology can be performed at 100°C through a simple one‐pot operation using in situ generated palladium nanoparticles. High catalytic activity, quick separation of catalyst from products using an external magnetic field and use of water as green solvent are attributes of this protocol.     

Synthesis and characterization of Fe3O4@SiO2–polymer-imid–Pd magnetic porous nanospheres and their application as a novel recyclable catalyst for Sonogashira–Hagihara coupling reactions

We demonstrate herein the modification of magnetic nanoparticles and their use as a magnetic nanocatalyst in direct coupling reactions of aryl halides with terminal alkynes. Magnetite particles were prepared by simple co-precipitation method in aqueous medium, and then Fe₃O₄@ SiO₂ nanosphere was synthesized by using nano-Fe₃O₄ as the core, TEOS as the silica source and PVA as the surfactant. Fe₃O₄@SiO₂ was coated with polymeric N-heterocyclic carbene/Pd. The samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, field emission scanning electron microscopy, dynamic light scattering, thermogravimetric analysis, vibration sample magnetometer and N₂ adsorption–desorption isotherm analysis. Poly (N-vinyl imidazole) functionalized Fe₃O₄@SiO₂ nanoparticle was found to be an efficient nanocatalyst in Sonogashira–Hagihara cross-coupling reactions. The nanocatalyst can be easily recovered by a magnetic field and reused for six runs without appreciable loss of 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.     

Effective one-pot synthesis of tetrahydrobenzo[b]pyran derivatives using nickel Schiff-base complex immobilized on iron oxide nanoparticles

Nickel Schiff-base complex immobilized on silica-coated Fe₃O₄ as a heterogeneous catalyst was designed and characterized by different techniques, such as Fourier transform infrared (FT-IR), X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), inductively coupled plasma (ICP) and vibrating sample magnetometry (VSM) thermogravimetric analysis (TGA), and Brunauer–Emmett–Teller (BET). The synthesized nanocatalyst has been explored as a new and efficient recyclable heterogeneous catalyst for the one-pot three-component synthesis of tetrahydrobenzo[b]pyran derivatives. The reaction proceeds smoothly to supply the respective products in excellent yields and low reaction times. The catalyst can be easily recovered by a magnetic field and reused for eight consecutive reaction cycles without significant loss of activity.     

Palladium nanoparticles supported on cucurbit[6]uril: an efficient heterogeneous catalyst for the Suzuki reaction under mild conditions

A new NC palladacycle was synthesized and supported on cucurbit[6]uril (CB[6]). The CB[6]‐supported palladium was used as an efficient nanocatalyst for the Suzuki reaction. In these reactions various aryl halides were reacted with arylboronic acids in H₂O–EtOH at both room temperature and 40 °C. The obtained Pd nanocatalyst exhibited excellent reactivity and stability in C ? C bond formation, which confirms that the catalyst is a completely active heterogeneous species. The Pd nanocatalyst was characterized using X‐ray diffraction, scanning electron microscopy and transmission electron microscopy. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis of 1-amidoalkyl-2-naphthol derivatives using a magnetic nano-Fe3O4@SiO2@Hexamethylenetetramine-supported ionic liquid as a catalyst under solvent-free conditions

Hexamethylenetetramine-functionalized silica-coated nano-Fe₃O₄ particles (MNPs@Hexamethylenetetramine) were prepared as a reusable heterogeneous catalyst using a facile process. The catalyst was synthesized and characterized using infrared, X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, and vibrating sample magnetometer. This magnetic nanocatalyst was employed as an efficient, reusable, and environmentally benign heterogeneous catalyst for the synthesis of amidoalkylnaphthol derivatives from a one-pot three-component condensation reaction of beta-naphthol, aldehydes, and amides in good to excellent yields, Moreover, this catalyst can be easily recovered by using a magnetic field and directly reused for at least seven runs without sign ificant loss of its activity.