Miyaura Reaction In Water Research Articles

Functionalization of Framboidal Phenylboronic Acid-Containing Nanoparticles via Aqueous Suzuki-Miyaura Coupling Reactions.

Polymeric nanoparticles with reactive functional groups are an attractive platform for drug carriers that can be conjugated with drugs through a cleavable covalent linkage. Since the required functional groups vary depending on the drug molecule, there is a need for development of a novel post-modification method to introduce different functional groups to polymeric nanoparticles. We recently reported phenylboronic acid (PBA)-containing nanoparticles (BNP) with a unique framboidal morphology created via one-step aqueous dispersion polymerization. Since BNPs have high surface area due to their framboidal morphology and contain a high density of PBA groups, these particles can be used as nanocarriers for drugs that can bind to PBA groups such as curcumin and a catechol-bearing carbon monoxide donor. To further explore the potential of BNPs, in this article we report a novel strategy to introduce different functional groups to BNPs via the palladium-catalyzed Suzuki-Miyaura cross-coupling reaction between the PBA groups and iodo- and bromo-coupling partners. We developed a new catalytic system that efficiently catalyzes Suzuki-Miyaura reactions in water without the need for an organic solvent, as confirmed by NMR. Using this catalyst system, we show that BNPs can be functionalized with carboxylic acids, aldehyde, and hydrazide groups while keeping their original framboidal morphology as confirmed via IR, alizarin red assay, and TEM. Furthermore, the potential of the functionalized BNP in drug delivery applications was demonstrated by conjugating the hydrogen sulfide (H2S)-releasing compound anethole dithiolone to carboxylic acid-functionalized BNPs and show their H2S-releasing capability in cell lysate.

Phosphorus ligand-free Suzuki–Miyaura reactions in the presence of ABTS at room temperature in water

A catalytic system for a phosphorus ligand-free Suzuki–Miyaura reaction in water at room temperature was disclosed. Ammonium 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulfonate) (ABTS) was an efficient promoter and acted both as a ligand and as a surfactant for the synthesis of biaryl compounds via the Suzuki–Miyaura reaction in water. The targeted biaryl architectures were achieved under mild conditions with high efficiency and good functional group tolerance.

Synthesis of glucoside-based imidazolium salts for Pd-catalyzed cross-coupling reaction in water

Sugar-based imidazolium salts (IMSs) represent an outstanding type of material making them eye-catching for a wide variety of applications. Herein, a series of glucoside-based IMSs (Glu-IMSs) combining glucoside and imidazolium head groups with different substituents were synthesized. The catalytic activities of these Glu-IMSs were evaluated by Pd-catalyzed Heck–Mizoroki and Suzuki–Miyaura reactions in water. Among them, the Glu-IMSs contain both –OH and NHCs coordination sites was found to be the most efficient ancillary ligand in comparison with other Glu-IMSs with just single NHCs coordination site. The HR-TEM analysis showed that the palladium nanoparticles stabilized by the Glu-IMSs with an average size of ~4.0 nm was formed in the reaction system, which may be act as an efficient real catalytic species. Under the optimized reaction conditions, a series of novel fluorine-cored organic small molecule functional materials were synthesized with favorable yields.

Suzuki–Miyaura Reaction in Water Catalyzed by Covalent Organic Framework-Supported Pd NPs

Suzuki–Miyaura Reaction in Water Catalyzed by Covalent Organic Framework-Supported Pd NPs

Pd–Co Nanoparticles Supported on Calcined Mg–Fe Hydrotalcites for the Suzuki–Miyaura Reaction in Water with High Turnover Numbers

We reveal the Suzuki–Miyaura reaction catalyzed by a Pd–Co nanocatalyst supported by Mg–Fe–CHT (calcined hydrotalcites). A variety of boronic acids and aryl halides were transformed into functionalized biphenyls in excellent yields using water as a solvent. The reaction could proceed under mild conditions with a simple operation and high turnover numbers. The excellent catalytic activities are reasonably attributed to the Co-doping, which forms a Pd–Co alloy on the surface of CHT.

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.

Aqueous Suzuki‐Miyaura Reaction with 0.6 Equiv. of Base: Green and Efficient Access to Biaryls and Unsymmetrical Terphenyls

AbstractA ligand‐free palladium‐catalyzed Suzuki–Miyaura reaction in water with 0.6 equiv. of base is described. This method enables the preparation of a variety of biaryls in high yields. Additionally, using bromo‐N‐methyliminodiacetic acid (MIDA) boronates as building block, one‐pot double Suzuki–Miyaura reaction has been achieved by controlling the amount of base, and various unsymmetrical terphenyls were prepared in moderate to good yields.

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.

Triazole-Containing Dendrimer-like Core Cross-Linked Micelles that Stabilize Pd Nanoparticles as Heterogenized Homogeneous Catalysts for Room-Temperature Suzuki-Miyaura Reactions in Water.

Featuring the advantages of both homogeneous (high activity) and heterogeneous (recyclability) catalysts, heterogenized homogeneous catalysts (e.g., dendrimer-stabilized metal nanoparticles) have received much attention in recent years. Here, we develop a new triazole-containing dendrimer-like core cross-linked micelle (DCCM) stabilized Pd nanoparticles as a highly efficient heterogenized homogeneous catalyst for the Suzuki-Miyaura reaction. Both arylboronic acids and iodobenzenes with diverse electronic properties performed with excellent reactivity under the mild conditions of room temperature, water as the sole solvent, and as low as 0.5 % catalyst loading. Importantly, the Pd@triazole-DCCMs can tolerate various functional groups well (e.g., alcohol, aldehyde, ester, acyl, amino, and cyano, etc.) and give the corresponding biphenyl products in high yields. Recycling experiments suggest that the new heterogenized homogeneous catalyst can be recovered simply and reused many times with negligible activity change.

Polyacrylamide-g-Reduced Graphene Oxide Supported Pd Nanoparticles as a Highly Efficient Catalyst for Suzuki–Miyaura Reactions in Water

To improve the dispersibility of graphene oxide (GO) in solvents, the grafting of polyacrylamide (PAM) from the GO surface was performed by redox polymerization system. The hydrophilic nature and high polarity of PAM have made effective dispersion of GO. Then, Pd nanoparticles (Pd NPs) were anchored on the surface of polyacrylamide grafted reduced graphene oxide nanosheets (PAM-g-rGO/Pd). The obtained nanocomposite was used for Suzuki–Miyaura cross-coupling reaction in an environmental friendly solvent under ambient conditions. The results showed that the prepared catalyst system exhibited high catalytic activity and stability which could be reused at least eight times without significant loss of its catalytic activity. This is mainly because of its small particle size, uniform dispersion of Pd NPs on the surface of PAM-g-GO/Pd, and lack of agglomeration of these nanoparticles during the preparation at room temperature.

Proximity Effect using a Nanocage Structure: Polyhedral Oligomeric Silsesquioxane‐Imidazolium Tetrachloro‐ palladate Salt as a Precatalyst for the Suzuki–Miyaura Reaction in Water

AbstractA polyhedral oligomeric silsesquioxane‐imidazolium tetrachloropalladate salt (POSS‐Imi‐PdCl4) was prepared by the reaction of a polyhedral oligomeric silsesquioxane‐imidazolium chloride salt (POSS‐Imi‐Cl) with PdCl2 and used as a pre‐catalyst for the Suzuki–Miyaura reaction in water at 100 °C at a low loading (0.08–0.16 mol %). Biphenyl compounds were isolated in high to excellent yields. A comparison of the POSS‐based catalyst with the corresponding catalyst without the nanocage structure (i.e., 1‐butyl‐3‐methylimidazolium tetrachloropalladate) highlighted the role of the POSS structure to reach higher yields in the Suzuki–Miyaura reaction. This result is ascribed to a proximity effect of the imidazolium moieties linked to the nanocage structure. Fresh and used catalytic materials were characterised by using X‐ray photoelectron spectroscopy and TEM.

Starch assisted palladium(0) nanoparticles as in situ generated catalysts for room temperature Suzuki–Miyaura reactions in water

The in situ generated PdNPs show excellent catalytic activity in Suzuki–Miyaura cross coupling reaction of electronically diversified arylbromides and arylboronic acids in water at room temperature with low catalyst loading.

In situ generated and stabilized Pd nanoparticles by N2,N4,N6-tridodecyl-1,3,5-triazine-2,4,6-triamine (TDTAT) as a reactive and efficient catalyst for the Suzuki–Miyaura reaction in water

The Suzuki–Miyaura coupling reaction was efficiently catalyzed by the in situ generated and stabilized Pd nanoparticles employing TDTAT in water.

ChemInform Abstract: Ohmic Heating‐Assisted Synthesis of 3‐Arylquinolin‐4(1H)‐ones by a Reusable and Ligand‐Free Suzuki—Miyaura Reaction in Water.

Potential bioactive 3-arylquinolin-4(1H)-ones were synthesized under ohmic heating using an efficient, reusable, and ligand-free protocol developed for the Suzuki–Miyaura coupling of 1-substituted-3-iodoquinolin-4(1H)-ones with several boronic acids in water using Pd(OAc)2 as a catalyst and tetrabutylammonium bromide (TBAB) as the phase transfer catalyst. Good substrate generality, ease of execution, short reaction time, and practicability make this method exploitable for the generation of libraries of B ring-substituted 3-arylquinolin-4(1H)-ones. After a simple workup, the Pd/catalyst-H2O-TBAB system could be reused for at least seven cycles without significant loss of activity.

Ohmic Heating-Assisted Synthesis of 3-Arylquinolin-4(1H)-ones by a Reusable and Ligand-Free Suzuki–Miyaura Reaction in Water

Potential bioactive 3-arylquinolin-4(1H)-ones were synthesized under ohmic heating using an efficient, reusable, and ligand-free protocol developed for the Suzuki-Miyaura coupling of 1-substituted-3-iodoquinolin-4(1H)-ones with several boronic acids in water using Pd(OAc)2 as a catalyst and tetrabutylammonium bromide (TBAB) as the phase transfer catalyst. Good substrate generality, ease of execution, short reaction time, and practicability make this method exploitable for the generation of libraries of B ring-substituted 3-arylquinolin-4(1H)-ones. After a simple workup, the Pd/catalyst-H2O-TBAB system could be reused for at least seven cycles without significant loss of activity.

Efficient Access to 2,6,8‐Trisubstituted 4‐Aminoquinazolines through Microwave‐Assisted One‐Pot Chemoselective Tris‐Suzuki–Miyaura or SNAr/Bis‐Suzuki–Miyaura Reactions in Water

AbstractAn efficient, sequential, one‐pot strategy for synthesizing polyfunctionalized quinazoline derivatives is presented. After selective amination of 6,8‐dibromo‐2,4‐dichloroquinazoline at the C‐4 position, 2,6,8‐trisubstituted 4‐aminoquinazoline derivatives were prepared through one‐pot chemoselective sequential tris‐Suzuki–Miyaura or SNAr/bis‐Suzuki–Miyaura reactions under microwave irradiation in an aqueous medium. This approach, used with a variety of boronic acids, affords polysubstituted quinazoline derivatives in good to excellent yields in only a few steps and in the environmentally benign solvent water.

ChemInform Abstract: Palladium Nanoparticles Supported in a Polymeric Membrane: An Efficient Phosphine‐Free “Green” Catalyst for Suzuki—Miyaura Reactions in Water.

AbstractThe title polymeric catalyst is successfully applied to Suzuki—Miyaura reactions of aryl iodides and bromides in water as the solvent.

ChemInform Abstract: Salicylaldoxime‐Functionalized Poly(ethylene glycol)‐Bridged Dicationic Ionic Liquid ([Salox‐PEG1000‐DIL][BF4]) as a Novel Ligand for Palladium‐Catalyzed Suzuki—Miyaura Reaction in Water.

AbstractThe catalytic system can be easily recovered and reused for at least five runs with only slight decrease in its activity.

A simple and efficient tetradentate Schiff base derived palladium complex for Suzuki–Miyaura reaction in water

A simple and efficient catalytic system based on Pd complex of tetradentate Schiff base ligands is found to be highly active (up to 99% isolated yield) for Suzuki–Miyaura reaction of aryl bromides with arylboronic acids in water at room temperature. Further the scope of this protocol has been extended to the Suzuki–Miyaura cross-coupling reaction of aryl chlorides with arylbronic acids in isopropanol.

Porous acrylate monolith supported Pd nanoparticles: highly active and reusable catalyst for Suzuki–Miyaura reaction in water

Palladium-Schiff-base functionalized porous methyl methacrylate-glycidyl methacrylate copolymer monoliths can be used for Suzuki–Miyaura reaction of aryl halides in water under aerobic conditions, giving biphenyl products with very high yield and the catalyst can be reused for several reaction cycles without significant loss in its activity.