A highly stable and efficient magnetically recoverable and reusable Pd nanocatalyst in aqueous media heterogeneously catalysed Suzuki C–C cross‐coupling reactions

Surface modification of Fe₃O₄ nanoparticles with triethoxyethylcyanide groups was used for the immobilization of palladium nanoparticles to produce Fe₃O₄/Ethyl‐CN/Pd. The catalyst was characterized using Fourier transform infrared, wavelength‐dispersive X‐ray, energy‐dispersive X‐ray and X‐ray photoelectron spectroscopies, field‐emission scanning electron and transmission electron microscopies, and X‐ray diffraction, vibrating sample magnetometry and inductively coupled plasma analyses. In this fabrication, cyano groups played an important role as a capping agent. The catalytic behaviour of Fe₃O₄/Ethyl‐CN/Pd nanoparticles was measured in the Suzuki cross‐coupling reaction of various aryl halides (Ar? I, Ar? Br, Ar? Cl) with phenylboronic acid in aqueous phase at room temperature. Interestingly, the novel catalyst could be recovered in a facile manner from the reaction mixture by applying an external magnet device and recycled seven times without any significant loss in activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Schiff base complex of palladium immobilized on magnetic nanoparticles: an efficient and recyclable nanocatalyst for CC coupling reactions

A Schiff base complex of palladium anchored on Fe₃O₄ magnetic nanoparticles as an efficient and magnetically reusable nanocatalyst is reported for C? C bond formation through Heck and Suzuki reactions. The catalyst was easily recovered and reused several times without significant loss of its catalytic efficiency or palladium leaching. The magnetic nanocatalyst was characterized using Fourier transform infrared and inductively coupled plasma atomic emission spectroscopies, thermogravimetric analysis, vibrating sample magnetometry, and transmission and scanning electron microscopies. Copyright © 2016 John Wiley & Sons, Ltd.     

Cu–S‐(propyl)‐2‐aminobenzothioate on magnetic nanoparticles: highly efficient and reusable catalyst for synthesis of polyhydroquinoline derivatives and oxidation of sulfides

Cu–S‐(propyl)‐2‐aminobenzothioate supported on functionalized Fe₃O₄ magnetic nanoparticles is reported as a reusable and highly efficient nanocatalyst for the one‐pot synthesis of polyhydroquinoline derivatives and also for selective oxidation of sulfides to sulfoxides. The prepared nanoparticles were characterized using Fourier transform infrared spectroscopy, vibrating sample magnetometry, thermogravimetric analysis, transmission and scanning electron microscopies, energy‐dispersive X‐ray spectroscopy, X‐ray diffraction, inductively coupled plasma atomic emission spectroscopy and atomic absorption spectroscopy. The nanocatalyst was easily recovered using an external magnet and reused several times without significant loss of its catalytic efficiency. Copyright © 2016 John Wiley & Sons, Ltd.     

New bis(N‐heterocyclic carbene) palladium complex immobilized on magnetic nanoparticles: as a magnetic reusable catalyst in Suzuki‐Miyaura cross coupling reaction

A new bis(N ‐heterocyclic carbene) (NHC) palladium complex supported on silica coated magnetic nanoparticles (MNPs) was prepared using the reaction of synthesized Pd‐NHC complex with MNPs. The Pd‐NHC complex was prepared using the reaction of a hydroxyl‐functionalized bis‐imidazolium ionic liquid. The Pd‐NHC organometallic complex was used as a heterogeneous recyclable and active catalyst in the Suzuki‐Miyaura reaction and various aryl halides were coupled with arylboronic acids in order to synthesize diverse biaryls in good to excellent yields. The prepared catalyst was characterized by use of some different microscopic and spectroscopic techniques including elemental analysis, FT‐IR spectroscopy, diffuse reflectance UV–Vis spectrophotometery, scanning electron microscopy (SEM), transmission electron microscopy (TEM), vibrating sample magnetometer (VSM) and X‐ray diffraction (XRD). The Pd‐NHC catalyst system is a magnetic reusable catalyst and it can be separated from the reaction mixture using an external magnetic field. The catalyst was reusable in the Suzuki‐Miyaura coupling reaction at least for 6 times without significant decreasing in its catalytic activity.     

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.     

Palladium–S‐propyl‐2‐aminobenzothioate immobilized on Fe3O4 magnetic nanoparticles as catalyst for Suzuki and Heck reactions in water or poly(ethylene glycol)

A moisture‐ and air‐stable heterogenized palladium catalyst was synthesized by coordination of palladium with S‐propyl‐2‐aminothiobenzamide supported on Fe₃O₄ magnetic nanoparticles. The prepared nanocatalyst was characterized using Fourier transform infrared, energy‐dispersive X‐ray and inductively coupled plasma atomic emission spectroscopies, X‐ray diffraction, vibrating sample magnetometry, transmission and scanning electron microscopies, dynamic laser scattering and thermogravimetric analysis. This catalyst could be dispersed homogeneously in water or poly(ethylene glycol) and further applied as an excellent nano‐organometal catalyst for Suzuki and Heck reactions. The catalyst was easily separated with the assistance of an external magnet from the reaction mixture and reused for several consecutive runs without significant loss of its catalytic efficiency or palladium leaching. The leaching of catalyst was examined using hot filtration and inductively coupled plasma atomic emission spectroscopy. Also, the effects of various reaction parameters on the Suzuki and Heck reactions are discussed. Copyright © 2016 John Wiley & Sons, Ltd.     

Green synthesis of palladium nanoparticles using Hibiscus sabdariffa L. flower extract: Heterogeneous and reusable nanocatalyst in Suzuki coupling reactions

An elementary and ecological method has been designed for the biosynthesis of palladium nanoparticles, through the utilization of aqueous extract of red tea (Hibiscus sabdariffa L.) as a reducing and stabilizing agent. The nanoparticles obtained were characterized through UV–visible spectroscopy, transmission election microscopy, X‐ray diffraction, Fourier transform infrared spectroscopy, scanning election microscopy, energy‐dispersive X‐ray analysis and inductively coupled plasma analysis. The nanoparticles with spherical shape and dimensions of approximately 10 nm were used as a heterogeneous catalyst for Suzuki coupling reactions under mild conditions. The high efficiency of the catalytic reaction was affirmed by the good yields of products, easy work‐up, absence of palladium leached from the support and smooth recovery of catalyst.     

Biosynthesis of palladium nanoparticles as a heterogeneous and reusable nanocatalyst for reduction of nitroarenes and Suzuki coupling reactions

A facile and green route for the synthesis of palladium nanoparticles (Pd‐NPs) was developed utilizing non‐toxic and renewable natural green tea extract as the reducing, stabilizing and capping agent. The as‐prepared Pd‐NPs@Oak Gum catalyst was characterized using UV–visible spectroscopy, X‐ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy and energy dispersive X‐ray spectroscopy. The Pd‐NPs@Oak Gum catalyst could be used as an efficient and heterogeneous catalyst for Suzuki coupling reactions between phenylboronic acid and a range of aryl halides containing iodo, bromo and chloro moieties and also for the reduction of nitroarenes using sodium borohydride in an environmental friendly medium. Excellent yields of products were obtained with a wide range of substrates and the catalyst was recycled multiple times without any significant loss of its catalytic activity. Copyright © 2016 John Wiley & Sons, Ltd.     

Highly efficient N‐Heterocyclic carbene–palladium complex‐catalyzed multicomponent carbonylative Suzuki reaction: novel practical synthesis of unsymmetric aryl ketones

Highly efficient and chemoselective N‐heterocyclic carbene palladium complexes‐catalyzed multicomponent carbonyltive Suzuki reaction with sodium tetraphenylborate used as phenylating reagent has been demonstrated in this article. Both electron‐rich and electron‐deficient aryl iodides gave unsymmetric aryl ketones in excellent yields. Copyright © 2007 John Wiley & Sons, Ltd.     

Palladium nanoparticles immobilized over Strawberry fruit extract coated Fe3O4 NPs: A magnetic reusable nanocatalyst for Suzuki-Miyaura coupling reactions

This paper develops a green method for in situ decorated of palladium nanoparticles over Fe₃O₄ nanoparticles, by utilizing Strawberry fruit extract and ultrasound irradiations, with no use of any toxic reducing agent. The structure's characterization is represented via diverse analytical methods such as FT-IR, FE-SEM, TEM, WDX, ICP, EDS and XXPS. Catalytic efficiency of magnetic Fe₃O₄@Strawberry/Pd nanocatalyst is investigated in production of different biphenyls with good turnover frequencies (TOF) and turnover numbers (TON) through Suzuki coupling reactions. Furthermore, the catalyst could be recovered and reused 7 runs without considerable palladium leaching or alteration in its performance.     

Synthesis and characterization of bromine source immobilized on diethylenetriamine‐functionalized magnetic nanoparticles: A novel,versatile and highly efficient reusable catalyst for organic synthesis

Bromine source immobilized on magnetic nanoparticles functionalized with diethylenetriamine was successfully synthesized and characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, vibrating sample magnetometry, thermogravimetric analysis and X‐ray diffraction. The catalytic activity in the synthesis of 2,3‐dihydroquinazoline‐4(1H )‐one and polyhydroquinoline derivatives and in Knoevenagel condensation was studied. The bromine catalyst can be magnetically recovered and reused several times without significant loss of its catalytic activity. All products were obtained in high to excellent yields.     

Pd nanoparticles immobilized on magnetic chitosan as a novel reusable catalyst for green Heck and Suzuki cross‐coupling reaction: In water at room temperature

A novel type of magnetically responsive chitosan nanocomposite was successfully synthesized as a green and high powerful palladium‐based heterogeneous catalyst and its efficiency in Heck and Suzuki cross‐coupling was evaluated. This catalyst promote a large library of functional substrates of these reactions under mild and sustainable conditions (water or ethanol as solvent, at room temperature, in significantly short reaction time (20 minutes)) and stand as recyclable, metal scavenging catalytic systems.     

Silver nanoparticles supported on ionic‐tagged magnetic hydroxyapatite as a highly efficient and reusable nanocatalyst for hydrogenation of nitroarenes in water

A novel chemically modified magnetic hydroxyapatite (MHAp) was prepared and used as support and stabilizer for the synthesis of silver nanoparticles. First, 1,4‐diazabicyclo[2.2.2]octane (DABCO) was successfully grafted onto the surface of MHAp, and then silver nanoparticles were homogeneously loaded on mesoporous MHAp‐DABCO (ionic‐tagged MHAp) nanocomposite by in situ chemical reduction of silver nitrate using sodium borohydride. The structure and properties of the resulting MHAp‐DABCO‐Ag nanocomposite were confirmed using various techniques. The catalytic activity of ionic‐tagged MHAp‐Ag nanocatalyst was investigated for the hydrogenation reaction of nitroarenes in aqueous media. The results reveal that the Ag‐containing inorganic–organic nanocomposite is highly efficient for the reduction of a wide range of aromatic nitro compounds under green conditions. The superparamagnetic nature of the nanocatalyst leads to its being readily removed from solution via application of a magnetic field, and it can be easily stored and reused.     

Biguanidine‐functionalized chitosan to immobilize palladium nanoparticles as a novel,efficient and recyclable heterogeneous nanocatalyst for Suzuki–Miyaura coupling reactions

Biguanidine‐functionalized chitosan was synthesized and combined with palladium nanoparticles to yield a recyclable, environmentally benign, heterogeneous catalytic system for the Suzuki–Miyaura C–C coupling reaction. The catalyst was characterized using various techniques. The catalyst was used in Suzuki cross‐coupling reactions of various aryl halides, including less reactive chlorobenzenes, with phenylboronic acid to give biaryls without any additive or ligand. A reusability test demonstrated that the catalyst was highly efficient even after six runs. Solid‐phase poisoning and leaching tests indicated that the catalyst has a heterogeneous nature. Copyright © 2016 John Wiley & Sons, Ltd.     

Pd embedded N,S co‐doped graphene wrapped core‐shell magnetic nanospheres: Engineered stable nanocatalyst for Suzuki couplings

Designed nitrogen and sulfur co‐doped graphene wrapped magnetic core‐shell supported Pd nanoparticles were synthesized through the following steps. Firstly, Fe₃O₄ was prepared, coated with silica and then functionalized with amine groups to create a positive charge on the structure for enhancing the interaction of the Fe₃O₄@SiO₂ with graphene oxide. Secondary, the pre‐catalyst wrapped with graphene to enhance adsorption of aromatic substrates through π–π stacking. Thirdly, graphene was doped with nitrogen and sulfur to increase the grafting of Pd in hybrid. Finally, Pd NPs were attached on the surface of pre‐engineered structure to produce Fe₃O₄@SiO₂@N,S‐wG@Pd which exhibited high performance in Suzuki reactions. This superior activity can be indexed to the incorporation of N and S atoms into graphene led to high anchoring and well‐dispersion of Pd NPs on the nanocomposite surface offering large amounts of active centers, that strongly increased the interaction between Pd and substrates to decreases Pd leaching.     

Nitro group reduction and Suzuki reaction catalysed by palladium supported on magnetic nanoparticles modified with carbon quantum dots generated from glycerol and urea

Glycerol and urea were used as green and cheap sources of carbon quantum dots (CQD) for modifying Fe₃O₄ nanoparticles (NPs). The obtained CQD@Fe₃O₄ NPs were used for the stabilization of palladium species and the prepared catalyst, Pd@CQD@Fe₃O₄, was characterized using various techniques. This magnetic supported palladium was applied as an efficient catalyst for the reduction of aromatic nitro compounds to primary amines at room temperature using very low palladium loading (0.008 mol%) and also for the Suzuki–Miyaura cross‐coupling reaction of aryl halides as well as challenging heteroaryl bromides and aryl diazonium salts with arylboronic acids and with potassium phenyltrifluoroborate. This magnetically recyclable catalyst was recovered and reused for seven consecutive runs in the reduction of 4‐nitrotoluene to p‐toluidine and for ten consecutive runs in the reaction of 4‐iodoanisole with phenylboronic acid with small decrease of activity. The catalyst reused in the Suzuki reaction was characterized using transmission electron microscopy, vibrating sample magnetometry and X‐ray photoelectron spectroscopy. Using experiments such as hot filtration and poisoning tests, it has been shown that the true catalyst works under homogeneous conditions according to the release–return pathway of active palladium species.     

Ionic liquid-containing polyethylene supported palladium: a green,highly efficient and stable catalyst for Suzuki reaction

The Suzuki coupling was carried out using a new, efficient and reusable polymer-supported Pd/IL catalyst (PEt@IL/Pd) under aqueous conditions. This catalyst was prepared through coacervation approach followed by treatment with Pd(OAc)₂. The FT-IR, SEM, TGA, TEM, XPS, ICP and EDX techniques were employed to characterize the PEt@IL/Pd. This catalyst exhibited high activity in the Suzuki coupling reaction under green conditions. Moreover, the catalyst could be recycled and reapplied for six times with no appreciable loss in its activity. The leaching test also showed high stability of catalytic Pd species under applied conditions.     

Fabrication of covalently functionalized mesoporous silica core–shell magnetite nanoparticles with palladium(II) acetylacetonate: application as a magnetically separable nanocatalyst for Suzuki cross‐coupling reaction of acyl halides with boronic acids

We report the preparation of supported palladium(II) acetylacetonate, Pd(acac)₂, coordinated by pendant acac groups, by reacting palladium acetate with acac‐functionalized doubly silica‐coated magnetic nanoparticles. The solid support consists of an amorphous silica‐coated (as magnetite protecting layer) magnetite core and a mesoporous silica shell. The magnetically separable palladium nanocatalyst is active for Suzuki cross‐coupling reaction of acyl halides with boronic acids. The catalyst is simply isolated from the reaction mixture that allows fast and efficient isolation of product and catalyst compared to traditional methods that generally make use of time‐ and solvent‐consuming procedures. Copyright © 2015 John Wiley & Sons, Ltd.     

Threonine stabilizer‐controlled well‐dispersed small palladium nanoparticles on modified magnetic nanocatalyst for Heck cross‐coupling process in water

We report the synthesis of magnetically separable Fe₃O₄@Silica‐Threonine‐Pd⁰ magnetic nanoparticles with a core–shell structure. After synthesis of Fe₃O₄@Silica, threonine as an efficient stabilizer/ligand was bonded to the surface of Fe₃O₄@Silica. Then, palladium nanoparticles were generated on the threonine‐modified catalyst. The threonine stabilizer helps to generate palladium nanoparticles of small size (less than 4 nm) with high dispersity and uniformity. Magnetically separable Fe₃O₄@Silica‐Threonine‐Pd⁰ nanocatalyst was fully characterized using various techniques. This nanocatalyst efficiently catalysed the Heck cross‐coupling reaction of a variety of substrates in water medium as a green, safe and inexpensive solvent at 80°C. The Fe₃O₄@Silica‐Threonine‐Pd⁰ catalyst was used for at least eight successful consecutive runs with palladium leaching of only 0.05%.