Miyaura Coupling Reaction In Water Research Articles

An efficient and recyclable palygorskite-supported palladium catalyst for Suzuki–Miyaura coupling reactions in water at room-temperature

An efficient and recyclable palygorskite-supported palladium catalyst for Suzuki–Miyaura coupling reactions in water at room-temperature

Micelle-Derived Palladium Nanoparticles for Suzuki–Miyaura Coupling Reactions in Water at Room Temperature

Despite the wide utility of colloidal palladium (Pd) nanoparticle (NP)-catalyzed Suzuki–Miyaura cross-coupling reactions in laboratory and industrial synthesis, the easy construction of colloidal Pd NPs and the detailed role of surfactants remain the focus of attention. Here, we present a simple and sustainable strategy to construct a nanoreactor by connecting micelles with Pd NPs. The strategy enables us to employ a pH-induced morphological transition of sugar-based surfactant aggregates, such as worm-like, spherical, and tubular micelles, to investigate the solubilization of organic substrates. Pd NPs are mainly synthesized by the reduction of phenylboronic acid, further stabilized by the sugar-based surfactant micelles. A kinetic model is established, and the apparent activation energy of this reaction in aqueous micellar solutions is determined to be 46.7 kJ/mol. Notably, the recycled aqueous reaction mixture containing the micelles and Pd NPs can be reused.

Immobilized Pd on a NHC functionalized metal–organic framework MIL‐101(Cr): an efficient heterogeneous catalyst in Suzuki−Miyaura coupling reaction in water

A novel Pd−NHC functionalized metal–organic framework (MOF) based on MIL‐101(Cr) was synthesized and used as an efficient heterogeneous catalyst in the C‐C bond formation reactions. Using this heterogeneous Pd catalyst system, the Suzuki−Miyaura coupling reaction was accomplished well in water, and coupling products were obtained in good to excellent yields in short reaction time. The Pd−NHC−MIL‐101(Cr) was characterized using some different techniques, including Fourier transform‐infrared, X‐ray diffraction, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy, inductively coupled plasma and elemental analysis. The microscopic techniques showed the discrete octahedron structure of MIL‐101(Cr), which is also stable after chemical modification process to prepare the catalyst system. The TEM images of the catalyst showed the existence of palladium nanoparticles immobilized in the structure of the catalyst, while no reducing agent was used. It seems that the NHC groups and imidazolium moieties in the structure of the MOF can reduce Pd (II) to Pd (0) species. This modified MOF substrate can also prevent aggregation of Pd nanoparticles, resulting in high stability of them in organic transformation. The Pd−NHC−MIL‐101(Cr) catalyst system could be simply extracted from the reaction mixture, providing an efficient synthetic method for the synthesis of biaryls derivatives using the aforementioned coupling reaction. The Pd−NHC−MIL‐101(Cr) catalyst could be recycled in this organic reaction with almost consistent catalytic efficiency.

Pd@COF-QA: a phase transfer composite catalyst for aqueous Suzuki–Miyaura coupling reaction

A COF-based phase transfer catalyst and its continuous flow-through reactor was prepared. The obtained Pd@COF-QA can highly promote the Suzuki–Miyaura coupling reaction in water under mild conditions even at gram scale level.

Palladium Comprising Dicationic Bipyridinium Supported Periodic Mesoporous Organosilica (PMO): Pd@Bipy–PMO as an Efficient Hybrid Catalyst for Suzuki–Miyaura Cross-Coupling Reaction in Water

In this study, we developed a novel catalysts consisting of periodic mesoporous organosilica functionalized with bipyridinium ionic liquid supported palladium. The physiochemical properties of the hybrid catalyst were investigated using Fourier transform infrared spectroscopy, small angle X–ray powder diffraction, field emission scanning electron microscope, transmission electron microscope, nitrogen adsorption–desorption analyses, and atomic absorption spectroscopy. The stabilized Pd species inside the mesochannels provided good catalytic efficiency for the Suzuki–Miyaura coupling reactions in water. The activity of the designed catalysts retained for several consecutive recycle runs. The stability, recoverability, and reusability of the designed heterogeneous catalyst were also studied under various reaction conditions.

Nanosized Bispyrazole-Based Cryptand-Stabilized Palladium(0) Nanoparticles: A Reusable Heterogeneous Catalyst for the Suzuki-Miyaura Coupling Reaction in Water.

A macrobicyclic cryptand with a long rigid cavity incorporating a chelating bispyrazole moiety in each of the three bridges was synthesized. The multiple chelating metal binding sites were utilized for the controlled synthesis and stabilization of ultrafine palladium nanoparticles (Pd NPs) of nearly ∼2 nm size. The as-synthesized Pd NPs were characterized by X-ray photoelectron spectroscopy, transmission electron microscopy, and powder X-ray diffraction. The well-dispersed cryptand-stabilized nanoparticles are found to catalyze the C-C bond-forming Suzuki-Miyaura reaction heterogeneously using water as a green solvent.

Palladium immobilized on functionalized hypercrosslinked polymers: a highly active and recyclable catalyst for Suzuki–Miyaura coupling reactions in water

Three palladium complexes were synthesized via an external cross-linking reaction and found to be effective heterogeneous catalysts for the Suzuki–Miyaura reaction.

1,2,3-Triazolylidene palladium complex with triazole ligand: Synthesis, characterization and application in Suzuki–Miyaura coupling reaction in water

Palladium complex containing 1,2,3-triazolylidene and a labile triazole moiety has been prepared and characterized. Simple azide alkyne click reaction using three fold excess of dibromoethane afforded 1-(2-bromoethyl)-4-phenyl-1H-1,2,3-triazole. The latter on dehydrobromination yields N-vinyl triazole (Ntzl) which is subsequently used for preparing its triazolium salt. Further, Ntzl–Pd–Ntzl complex was prepared from triazole by simple palladation which underwent a ligand substitution reaction when treated with in situ generated triazolylidene to form Ctzl–Pd–Ntzl type complex. This mixed palladium complex was found to be highly effective in catalyzing Suzuki–Miyaura coupling reaction between aryl halides and aryl boronic acids in water at room temperature with very low catalyst loading.

Journey on Greener Pathways via Synthesis of Pd/KB Polymeric Nanocomposite as a Recoverable Catalyst for the Ligand-Free Oxidative Hydroxylation of Phenylboronic Acid and Suzuki–Miyaura Coupling Reaction in Green Solvents

This paper reports a new and straightforward technique for the preparation of catalytically active palladium nanoparticle (Pd NPs) supported on the polymer surface derived from virgin polythene (Kaldnes Bio media filter) (Pd/KB nanocomposite). The morphology, structure and composition of Pd/KB nanocomposite were characterized by SEM, TEM, XRD, EDX and UV–Vis spectroscopy. The as-prepared catalyst presented excellent catalytic activity for the ligand-free oxidative hydroxylation of phenylboronic acid and Suzuki–Miyaura coupling reaction in water and ethanol as green solvents. In addition, the catalyst could be easily separated from the reaction mixture and reused four times with no loss of activity. The advantages of this eco-friendly protocol are using the cheap, clean, and nontoxic precursors, simple reaction setup, high yield of products and elimination of ligand and homogeneous catalysts.

Functionalized Bis(triazolyl)phenylmethanol–palladium(II) Catalysts for Cross Coupling Reactions in Water

AbstractPdII‐bis(triazolyl)phenylmethanol complexes bearing different groups (i. e., H, OMe, OH, COOH) directly attached to the benzyl rings were explored as precatalysts for copper‐free Sonogashira and Suzuki–Miyaura coupling reactions in water. Crystal structures reveal a bidentate N,N binding mode of the bis(triazolyl) ligands affording a distorted square planar PdII complexes. With the exception of the phenol‐substituted bis(triazolyl) ligands, the other three Pd complexes exhibited high activities toward Suzuki–Miyaura coupling reactions. Transmission electron microscopy (TEM) study and PPh3 poisoning experiments confirm that bis(triazoly)‐stabilized Pd nanoparticles (Pd NPs) were generated in situ during the catalytic reactions and involved as one of the active catalytic species in the Suzuki–Miyaura cross coupling.

Mercaptoaryl‐Oxazoline Complexes of Palladium and Their High Activities as Catalysts for Suzuki–Miyaura Coupling Reactions in Water

The synthesis, spectroscopic characterization, and catalytic activities of a series of PdII complexes bearing the monoanionic, bidentate ligand 2‐(2‐thiophenyl)‐4,4‐dimethyloxazoline (S‐Phoz) are reported. These complexes were used as precatalysts for Suzuki–Miyaura coupling reactions under aqueous conditions. The dimers [{PdX(S‐Phoz)}2] (X = Cl, Br, I; 1–3) were treated with the N‐heterocyclic carbene (NHC) ligand 1,3‐bis(2,4,6‐trimethylphenyl)imidazol‐2‐ylidene (IMes) to afford the mononuclear complexes [PdX(S‐Phoz)(IMes)] (X = Cl, Br, I; 4–6). The σ‐donor/π‐acceptor complexes [PdCl(S‐Phoz)(EPh3)] (E = P, As, Sb; 7–9) were synthesized to evaluate the influence of a second donor ligand on the catalytic activity. Within the [PdCl(S‐Phoz)L] series, the activity trend for L follows the trend PPh3 > IMes ≈ AsPh3 > SbPh3. The sulfur‐bridged dinuclear complexes 1–3 are highly active for the benchmark coupling of p‐bromoacetophenone with phenylboronic acid and exhibit turnover frequencies (TOFs) of up to 16000 h–1. DFT and G0W0 calculations were performed to rationalize the facile reduction and, hence, excellent activities of the dinuclear complexes.

Suzuki–Miyaura coupling reaction in water in the presence of robust palladium immobilized on modified magnetic Fe3O4 nanoparticles as a recoverable catalyst

Aryl halides and especially inactive aryl chlorides were coupled to benzenoid aromatic rings in a Suzuki–Miyaura coupling reaction in the absence of organic solvents and toxic phosphine ligands. The reaction was catalysed by a recoverable magnetic nanocatalyst, Pd@Fe3O4, in aqueous media. This method is green, and the catalyst is easily removed from the reaction media using an external magnetic field and can be re‐used at least 10 times without any considerable loss in its activity. The catalyst was characterized using scanning and transmission electron microscopies, thermogravimetric analysis, inductively coupled plasma spectroscopy, Fourier transform infrared spectroscopy, CHN analysis, X‐ray diffraction and vibrating sample magnetometry.

Porphyrin‐based polymer‐supported palladium as an excellent and recyclable catalyst for Suzuki–Miyaura coupling reaction in water

A porphyrin‐based polymer with high surface area was synthesized using 5,10,15,20‐tetraphenylporphyrin through a one‐pot Friedel–Crafts alkylation reaction. Pd(II) was successfully supported on this polymer. This strategy provides an easy approach to produce highly stable Pd–porphyrin‐based polymer. The resulting Pd catalyst was characterized using Fourier transform infrared and X‐ray photoelectron spectroscopies, thermogravimetric analysis, scanning and transmission electron microscopies and N2 adsorption–desorption measurements. This porphyrin‐based polymer‐supported Pd was used as a heterogeneous catalyst for Suzuki–Miyaura coupling reaction in water. The results demonstrated that this Pd catalyst indeed exhibited excellent catalytic activity and recycling performance in water, even for inactive aryl chloride substrate. A new heterogeneous strategy for catalyzing the Suzuki–Miyaura reaction in water is provided.

Plant leaves as natural green scaffolds for palladium catalyzed Suzuki–Miyaura coupling reactions

This work presents a novel approach of using natural plant leaf surfaces having intricate hierarchical structures as scaffolds for Pd nanoparticles and demonstrated it as a Green dip catalyst for Suzuki–Miyaura coupling reactions in water. The influence of the topographical texture of the plant leaves on the deposition and catalytic properties of Pd nanoparticles are presented and discussed. The catalytic activity can be correlated to the surface texture of the leaves, wherein it has been found that the micro/nanostructures present on the surface strongly influence the assembly and entrapment of the nanoparticles, and thereby control aggregation and leaching of the catalysts. This approach can provide insights for the future design and fabrication of bioinspired supports for catalysis, based on replication of leaf surfaces.

Preparation of Water-Dispersible Palladium Nanoparticles Stabilized by Carbon–Palladium Bonds and Application to Suzuki–Miyaura Coupling in Water

Abstract Water-dispersible palladium nanoparticle catalysts have been prepared using palladium–carbon covalent bonds. They worked as an excellent catalyst for Suzuki–Miyaura coupling reaction in water. Even though the particle size of Pd nanoparticles was much larger than the previously reported ones, they showed a very good catalytic activity for the coupling reaction.

Biosynthesis of palladium nanoparticles using Rosa canina fruit extract and their use as a heterogeneous and recyclable catalyst for Suzuki–Miyaura coupling reactions in water

A facile and green route for the synthesis of palladium nanoparticles was developed utilizing non‐toxic and renewable natural Rosa canina fruit extract as the reducing, stabilizing and capping agent, and they were applied as a heterogeneous catalyst for Suzuki coupling reactions between phenylboronic acid and a range of aryl halides containing iodo, bromo and chloro moieties in water under moderate reaction conditions. The structural investigation of the generated nanoparticles was performed with UV–visible spectroscopy, transmission electron microscopy, X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and energy‐dispersive X‐ray analysis. The method has some advantages such as high yields, efficiency, elimination of surfactant, chemical reductants, ligand and organic solvent, economic, cleaner reaction profiles, heterogeneous catalysis, simple methodology and easy workup. The catalyst can be recovered and reused seven times without any significant decrease in catalytic activity. Copyright © 2016 John Wiley & Sons, Ltd.

A reusable heterogeneous catalyst without leaking palladium for highly-efficient Suzuki–Miyaura reaction in pure water under air

We prepared a novel palladium catalyst Pd@FSM based on mesoporous silica functionalized with Pd2+ fluorescent probe. Pd@FSM shows high catalytic activity and excellent reusability in Suzuki–Miyaura coupling reaction in water under air.

Green synthesis of a palladium–polyaniline nanocomposite for green Suzuki–Miyaura coupling reactions

One pot synthesis of the pd–polyaniline nanocomposite and its catalytic activity in Suzuki–Miyaura coupling reaction in water.

Graphene oxide supported Au nanoparticles as an efficient catalyst for reduction of nitro compounds and Suzuki–Miyaura coupling in water

This paper reports on the synthesis of graphene oxide supported Au nanoparticles and their application as a separable catalyst for ligand-free Suzuki–Miyaura coupling reactions in water and reduction of nitro compounds. The catalyst was characterized using powder XRD, BET, FT-IR, Raman, SEM and EDS. This method has the advantages of high yields, simple methodology, and elimination of ligand, organic solvent and homogeneous catalysts and easy work up. Interestingly, the novel catalyst could be recovered in a facile manner from the reaction mixture and recycled several times without any significant loss of catalytic activity.

Magnetic Pd/Fe3O4/reduced-graphene oxide nanohybrid as an efficient and recoverable catalyst for Suzuki–Miyaura coupling reaction in water

Palladium nanoparticles were supported on magnetic Fe3O4/reduced-graphene oxide(Fe3O4/r-GO) nanohybrid by reduction of dichloropalladium (II) complex in water. Pd/Fe3O4/r-GO nanohybrid was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction, and transmission electron microscopy (TEM). Our study shows that Pd/Fe3O4/r-GO nanohybrid was suitable for Suzuki–Miyaura carbon–carbon coupling reaction in water. Compared to the classical reactions, this method consistently has the advantages of green solvent, short reaction times, little catalyst loading, high yields, easy magnetically separation and reusability of the catalyst. Furthermore, Pd/Fe3O4/r-GO nanohybrid shows a high catalytic activity toward aryl chloride derivatives.