Miyaura Cross-coupling Reaction In Water Research Articles

Structural features influencing the activity of bis-biguanide ligands in the Suzuki–Miyaura cross-coupling reaction in neat water

Catalytic reactions play an integral role in the development of green chemistry. Herein, we report new bis-biguanide compounds containing alkyl and aryl spacers as ligands for the Suzuki–Miyaura cross-coupling reaction in water. These ligands show similar catalytic activity to metformin independently of the nature of the spacer between the two biguanide units.

Evaluation of Nitrogen-Based Polymeric Heterogeneous Catalysts for the Suzuki–Miyaura Cross-Coupling Reaction in Water

As environmental issues continuously increase, the development of effective and eco-friendly catalytic systems in organic chemistry is of great importance. To achieve this goal, two representative ...

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.

A urea-modified tryptophan based in situ reducing and stabilizing agent for the fabrication of gold nanoparticles as a Suzuki-Miyaura cross-coupling catalyst in water.

Urea-modified tryptophan has been used as an in situ reducing and stabilizing agent for the fabrication of gold nanoparticles in water. The tryptophan side chain NH has been used for the reduction of gold ions in HAuCl4 to metallic gold and carboxylic acid functionality helps to stabilize the gold nanoparticles. This was confirmed by a controlled reaction with urea-modified leucine which failed to form any gold nanoparticles. The resultant gold nanoparticles have been characterized by various spectroscopic techniques such as UV-visible spectroscopy, FT-IR spectroscopy and microscopic techniques such as FE-SEM and TEM. Moreover, we have shown that the urea-modified tryptophan stabilized gold nanoparticles catalyze the Suzuki–Miyaura cross-coupling reaction. The gold nanoparticle catalyzed Suzuki–Miyaura cross-coupling reaction between 4-bromobenzoic acid and phenylboronic acid in water provides 92% yield in 40 minutes. The high efficiency exhibited by the gold nanoparticle catalyst was effectively translated to a large number of Suzuki–Miyaura reactions between halides with phenylboronic acid. The results may inspire further research on gold nanoparticles catalysis in water.

An efficient and simple imidazole-hydrazone ligand for palladium-catalyzed Suzuki-Miyaura cross-coupling reactions in water under infrared irradiation

A highly efficient catalytic system based on Pd(OAc)2 and an imidazole-hydrazone ligand has been developed for Suzuki–Miyaura cross-coupling reaction in water under aerobic conditions using IR-irradiation. The system can tolerate a wide range of functionalized arylboronic acids and aryl halides. Furthermore, this protocol is also applicable for hetero-aryl bromides.

External cross-linked sulfonate-functionalized N-heterocyclic carbenes: an efficient and recyclable catalyst for Suzuki–Miyaura reactions in water

A sulfonate-functionalized N-heterocyclic carbene (NHC) was successfully attached to a hyper-cross-linked polymer via an external cross-linking reaction. The structure of Poly-BBIS was confirmed by FTIR spectroscopy, TEM, FESEM, and BET. The Poly-BBIS show a large surface areas (up to 563 m2 g−1) and hydrophilicity, as well as abundant micro-mesoporous, tunable and versatile active sites. The catalytic activity of the Pd derivative Poly-BBIS-Pd2+ was examined for Suzuki–Miyaura cross-coupling reactions in water, followed by an investigation of the reaction mechanism. The Poly-BBIS-Pd2+ gives a yield of 98% for the reaction between bromobenzene and phenylboronic acid with a loading of 0.057 mmol % Pd in water after approximately 2 h. Also, the catalyst can be reused for 5 times without significant loss of activity. This work highlights a low-cost route to the synthesis of heterogeneous catalysts based on hydrophilic sulfonate-functionalized NHC polymers for the Suzuki–Miyaura cross-coupling reaction in water.

Reusable Palladium N-Heterocyclic Tetracarbene for Aqueous Suzuki–Miyaura Cross-Coupling Reaction: Homogeneous Catalysis and Heterogeneous Recovery

A pH-responsive Pd(II) N-heterocyclic tetracarbene complex synthesized by a solvothermal method was reported. It can be a highly active reusable catalyst to homogeneously catalyze the Suzuki–Miyaura cross-coupling reaction in water and can be heterogeneously recovered by simply adjusting the pH value of the aqueous reaction media.

The Arrangement of Two N-Heterocyclic Carbene Moieties in Palladium Pincer Complexes Affects Their Catalytic Activity towards Suzuki–Miyaura Cross-Coupling Reactions in Water

Abstract Palladium complexes with pincer ligands containing one pyridine and two N-heterocyclic carbene units with acetyl-protected d-glucopyranosyl groups in C-C-N and C-N-C arrangements were synthesized. The complexes form diastereomers due to the twisted pincer ligands and chiral d-glucopyranosyl units. The diastereomers of the C-C-N complex are in equilibrium in solution, whereas only one of the diastereomers of the C-N-C complex forms kinetically. Deprotection of the acetyl groups in the ligands afforded water-soluble complexes with one of the hydroxide groups in the d-glucopyranosyl groups coordinated to the metal ion. In CD3OD, the deprotected complex with the C-N-C ligand gradually decomposed, whereas that with the C-C-N ligand was stable at room temperature. The complexes catalyzed Suzuki–Miyaura cross-coupling reactions in water with turnover numbers of 75,000 for the C-C-N and 8,900 for C-N-C complexes. The C-C-N complex was not deactivated by the addition of metallic Hg meaning that the active species is the complex itself or its derivatives having the pincer ligand. On the other hand, the C-N-C complex exhibited no catalytic activity for the coupling reaction in the presence of metallic Hg, meaning that the active species are heterogeneous catalysts, such as Pd nanoparticles.

ChemInform Abstract: Recent Advances in the Palladium Catalyzed Suzuki‐Miyaura Cross‐Coupling Reaction in Water

AbstractReview: 112 refs.

Recent Advances in the Palladium Catalyzed Suzuki–Miyaura Cross-Coupling Reaction in Water

The palladium-catalyzed Suzuki–Miyaura cross-coupling reaction of organic halides with boronic acids is one of the most versatile methods for the synthesis of biaryls. Green chemistry is a rapidly developing new field that provides us a proactive avenue for the sustainable development of future science and technologies. When designed properly, clean chemical technology can be developed in water as a reaction medium. The technologies generated from such green chemistry endeavours may often be cheaper and more profitable. This review covers the literature on palladium-catalysed the Suzuki–Miyaura cross-coupling reaction in water.

Syntheses and Catalytic Ability of Sugar-Incorporated N-Heterocyclic Carbene Pincer Pd Complexes Possessing Various N-Substituents

Abstract Exploration of catalysts for organic reactions in water, which is a nontoxic and nonexplosive liquid, has been studied to achieve environmentally friendly chemical processes. For such a purpose, we utilized click chemistry to incorporate sugar units into transition-metal complexes affording water-soluble complexes. In this study, a series of palladium complexes with C–C–N pincer ligands, each of which consisted of two N-heterocyclic carbenes (NHCs) and a triazole moiety with a d-glucopyranosyl unit were synthesized. These complexes possess various N-substituents, namely, methyl, isopropyl, benzyl, or d-glucopyranosyl units on the terminal NHC moieties. The diastereoselectivity in the formation of the complexes and their catalytic ability toward the Suzuki–Miyaura cross-coupling reactions in water exhibited clear N-substituent effects. The tridentate ligand with an acetylated d-glucopyranosyl unit on the terminal NHC moiety led to high diastereoselectivity in the formation of its complex, while each of the other ligands with achiral substituents on the terminal NHC units afforded both of the diastereomers with low selectivity. Catalytic reactions using the complexes were examined for the Suzuki–Miyaura cross-coupling reactions of phenylboronic acid and 4′-bromoacetophenone in water. The complex possessing an isopropyl group on the terminal NHC moiety exhibited excellent catalytic activity with TON (800000), which is comparable to the best value reported for a similar reaction.

Phenylphosphinacalix[3]trifuran: synthesis, coordination and application in the Suzuki–Miyaura cross-coupling reaction in water

Phenylphosphinacalix[3]trifuran and supramolecular assemblies with palladium have been synthesized. Phenylphosphinacalix[3]trifuran affords turnover numbers as high as 3.05 × 107 in Suzuki–Miyaura cross-coupling reactions in pure water.

Facile-prepared sulfonated water-soluble PEPPSI-Pd-NHC catalysts for aerobic aqueous Suzuki–Miyaura cross-coupling reactions

Four sulfonated water-soluble PEPPSI-Pd-NHC complexes (2a–2d) are prepared in a straightforward two-step synthesis. Their activities have been examined in Suzuki–Miyaura cross-coupling reactions in water under air. Complex 2d, bearing a 2,6-diisopropylphenyl substituent, shows the best catalytic activity and a variety of aryl bromides with a catalyst loading of 0.1 mol% can be efficiently activated even at room temperature. The catalyst is recyclable and can be employed in at least four consecutive runs without significant loss in performance. Furthermore, TEM analysis, kinetic studies and mercury poisoning experiments indicate that Pd nanoparticles are formed during the reactions.

Polystyrene-supported palladium(II) N,N-dimethylethylenediamine complex: A recyclable catalyst for Suzuki–Miyaura cross-coupling reactions in water

The polystyrene-supported Pd(II) N,N-dimethylethylenediamine complex was prepared and characterized by various techniques, including Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), atomic absorption spectroscopy (AAS), and thermal analysis (TG-DTA). This heterogeneous Pd(II) catalyst works efficiently for the Suzuki–Miyaura coupling of arylboronic acids with aryl bromides in aqueous medium. The effect of base, and additives for the C–C coupling reactions were reported. Further, the catalyst can be easily recovered quantitatively by simple filtration and reused up to five times without significant loss in its catalytic activity.

Silica-acac-supported palladium nanoparticles as an efficient and reusable heterogeneous catalyst in the Suzuki–Miyaura cross-coupling reaction in water

Supported Pd nanoparticles on acetyl acetone modified silica gel was prepared and its catalytic application in the Suzuki–Miyaura reaction of various aryl halides with phenylboronic acid was investigated. The reaction was carried out in water as solvent under green conditions in the presence of NaHCO3as the base. The catalyst was characterized by a combination of powder XRD, XPS, TEM and SEM. The catalyst is not sensitive to air and moisture, so reactions were carried out without using inert atmosphere. The catalyst can be reused up to six times without significant loss of catalyst activity. The cumulative turnover number (TON) over six runs is 13525.

Suzuki–Miyaura cross-coupling reactions in water using in situ generated palladium(II)–phosphazane complexes

Abstract The phosphazane derivatives ( L 1–3 ) were readily obtained by reaction of different ratios of PCl 3 and PhNH 2 . The L 1–3 derivatives were found to be efficient ligands in the palladium-catalyzed Suzuki C C coupling reactions in water. It was determined that with the use of L 1–3 /Pd(OAc) 2 system as a catalyst, aryl halides undergo Suzuki cross-couplings with arylboronic acids to give the desired products in moderate to excellent yields.

Water-Soluble Palladium Click Chelating Complex: An Efficient and Reusable Precatalyst for Suzuki-Miyaura and Hiyama Reactions in Water

A water-soluble ionic palladium(II) nitrogen-containing chelating complex, [palladium(II) 1-(4-N,N′,N′′-trimethylbutylammonium)-4-(2-pyridyl)-1H-1,2,3-triazole dichloride] chloride (3), was prepared through the click reaction of 1-chloro-4-bromobutane, sodium azide, and 2-ethynylpyridine, followed by the quarternization of Me3N and subsequent reaction with [Pd(cod)Cl2] (cod=1,5-cyclooctadiene). The catalytic performances of complex 3 were preliminarily evaluated through Suzuki–Miyaura and Hiyama cross-coupling reactions of aryl bromides; excellent catalytic activity in water was observed. TEM analysis revealed that small palladium nanoparticles (NPs) with a narrow size distribution were formed after the catalytic reaction. The NPs were stabilized by the synergetic effect of coordination and electrostatic interactions from the ionic, bidentate, nitrogen-containing ligand; no palladium black was detected after the aqueous solution of palladium NPs was stored in air for months. The use of 3 as a precursor in the formation of palladium NPs was further explored by using NaBH4 and hydrogen as reductive reagents. The resulting NPs displayed different sizes, surface properties, and catalytic performances in the Suzuki–Miyaura cross-coupling reaction in water.

Synthesis and characterization of new potentially hydrosoluble pincer ligands and their application in Suzuki–Miyaura cross-coupling reactions in water

Three water soluble pincer ligands, 2,6-bis[(diethanolamine)methyl]pyridine hydrobromide (1:2) (1), 3,11,17,18-Tetraazatricyclo[11.3.1.15,9]octadeca-1(17),5,7,9(18),13,15-hexaene,3,11-bis(dihydroxymethylmethyl) hydrobromide (1:2) (2), and 1,3-bis[(diethanolamine)methyl]benzene (3) were synthesized and unequivocally characterized by a number of analytical techniques including single crystal X-ray diffraction analyses. Mixtures of these ligands with PdCl2 proved to be efficient in catalyzing the Suzuki–Miyaura cross couplings in water. Being the most efficient system that including ligand (1). Further experiments using this catalytic system were performed to assess the effects of varying temperature, reaction times, and nature of the base, finding the optimal operational conditions of this system.

Use of Polymer-Supported Terpyridine Palladium Complex for Suzuki–Miyaura Cross-Coupling Reaction in Water and the Synthesis of 2,6-Disubstituted Pyrimidines

Use of Polymer-Supported Terpyridine Palladium Complex for Suzuki–Miyaura Cross-Coupling Reaction in Water and the Synthesis of 2,6-Disubstituted Pyrimidines

Palladium nanoparticles immobilized by click ionic copolymers: Efficient and recyclable catalysts for Suzuki–Miyaura cross-coupling reaction in water

Click reaction of alkyne-functionalized imidazolium salts with azide-containing copolymers gave rise to the click ionic copolymers, subsequent complexation with palladium acetate and reduction using NaBH 4 gave rise to palladium nanoparticles (NPs). The NPs demonstrated high catalytic activity in Suzuki–Miyaura cross-coupling reaction of aryl bromides in pure water. The catalytic system can be used at least five times, no obvious loss of catalytic activity is observed after the reaction. The palladium nanoparticles immobilized by click ionic copolymers exhibit high catalytic stability and recyclability in Suzuki–Miyaura cross-coupling reaction in water. ► Click ionic copolymers are efficient protective agents of palladium NPs. ► The NPs are stabilized by synergetic effect of coordination, electrostatic and steric interactions. ► Suzuki–Miyaura cross-coupling reactions are performed in air and water. ► Palladium NPs can be used at least five times without obvious aggregation.