Suzuki-Miyaura Coupling In Water Research Articles

Nickel-Catalyzed Suzuki-Miyaura Coupling in Water for the Synthesis of 2-Aryl Allyl Phosphonates and Sulfones.

An operationally simple and green protocol using a NiSO4·6H2O/cationic 2,2'-bipyridyl ligand system as a water-soluble catalyst for the coupling of arylboronic acids with (2-haloallyl)phosphonates and (2-haloallyl)sulfones in water under air was developed. The reaction was performed at 120 °C with arylboronic acids (2 mmol) and (2-haloallyl)phosphonates or sulfones (1 mmol) in the presence of 5 mol % of the Ni catalytic system in a basic aqueous solution for 1 h, giving the corresponding 2-aryl allyl phosphonates or sulfones in good to excellent yields. This reaction features the use of an abundant transition metal as a catalyst in water and exhibits high functional group tolerance, rendering it an eco-friendly procedure.

Continuous-Flow Suzuki-Miyaura Coupling in Water and Organic Solvents Promoted by Blends of Stabilized Convoluted Polymeric Palladium Catalysts and Polymeric Auxiliary Materials.

Given that heterogeneous palladium-catalyzed C-C bond formation reactions under continuous-flow conditions are well suited for the efficient and safe production of pharmaceuticals and functional materials, the development of active and durable catalysts for this purpose is a matter of high practical significance. Here, a previously established molecular convolution methodology was used to synthesize catalysts for Suzuki-Miyaura coupling under flow conditions by blending convoluted polymeric palladium catalysts (prepared from copolymers of 4-vinylpyridine and 4-tert-butylstyrene) and crosslinked polymeric auxiliary materials (prepared from copolymers of divinylbenzene and 4-tert-butylstyrene). The optimal catalyst exhibited high performance and durability and allowed numerous biaryl products such as liquid-crystalline materials, organic electroluminescent materials, and pharmaceuticals to be continuously synthesized with turnover frequencies of up to 238 h-1 . In a demonstration of practical utility, the developed catalytic system was used for the continuous synthesis of two pharmaceuticals (felbinac and fenbufen) in water as the sole solvent.

Proof of Concept: Interface of Recyclable Organogels with Embedded Palladium Nanoparticles Catalyzing Suzuki-Miyaura Coupling in Water at Room Temperature.

A sustainable approach for C–C cross-coupling reaction at room temperature in water has been developed to avoid tedious Pd separation, reduce the carbon footprint, and save energy. Another important aspect is the catalyst recycling and easy product separation. α,γ-Hybrid peptides were designed to selectively use as a ligand for C–C cross-coupling catalysts as well as to form organogels. The peptides form antiparallel sheet-like structures in the solid state. The peptide containing m-aminobenzoic acid, glycine, and dimethylamine forms a whitish gel in toluene, and co-gelation with Pd(OAc)2 results in light brown gel, which acts as a biphasic catalyst for Suzuki–Miyaura cross-coupling at room temperature in water by mild shaking. The organic–inorganic hybrid gel was characterized by rheology, field-emission scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray analyses. On completion of the cross-coupling reaction, the basic aqueous layer (containing products) above the gel can be simply decanted and the intact organic–inorganic hybrid gel can be recycled by topping-up fresh reactants multiple times. The reaction permitted a range of different substitution patterns for aryl and heterocyclic halides with acid or phenol functional groups. Both electron-donating- and electron-withdrawing-substituted substrates exhibited good results for this transformation. The findings inspire toward a holistic green technology for Suzuki–Miyaura coupling reaction and an innovative avenue for catalyst recycling and product isolation.

An efficient Pd(II)-(2-aminonicotinaldehyde) complex as complementary catalyst for the Suzuki-Miyaura coupling in water

An efficient new Pd(II)-(2-aminonicotinaldehyde)-catalyzed Suzuki-Miyaura coupling of the aryl halides (Br, Cl and I) and organoboronic acids at moderate temperature in water is described. Low catalyst loading, easy accessibility, being an air-stable catalyst, functional group compatibility, and water as the reaction medium are some of the key features of this synthetic method. This protocol is also applicable for gram scale.

Efficient synthesis of organic semiconductors by Suzuki–Miyaura coupling in an aromatic micellar medium

New PiNap-750M π-surfactant enables unprecedented performances in the preparation of BTBT derivatives and other organic semiconductors by Suzuki-Miyaura coupling in water and at room temperature.

Coordination-polymer anchored single-site ‘Pd-NHC’ catalyst for Suzuki-Miyaura coupling in water

A single-site, heterogeneous Pd–NHC-based catalyst was designed on a coordination polymer platform via metal-terpyridine interaction. The catalyst was successfully applied in Suzuki-Miyaura coupling in water showing good activity and reusability. SYNOPSIS A single-site, heterogeneous Pd–NHC-based catalyst anchored on a coordination polymer platform was successfully applied in Suzuki-Miyaura coupling in water showing good activity and reusability.

ChemInform Abstract: O‐Aryloxime Ether Analogues as Novel and Efficient Ligands for Palladium‐Catalyzed Suzuki—Miyaura Coupling in Water.

AbstractA simple combination consisting of PdCl2 and O‐aryl oxime ethers is found to catalyze the Suzuki—Miyaura coupling of aryl bromides with arylboronic acids in water at room temperature (27°C).

Suzuki-Miyaura Coupling in Water with Pd@SBA-15©

Suzuki-Miyaura Coupling in Water with Pd@SBA-15©

Suzuki-Miyaura Coupling in Water with Pd@CSP

Palladium nanoparticles, which were supported on amphiphilic colloidal carbon spheres, catalyzed the Suzuki-Miyaura coupling of aryl halides 1 with arylboronic acids 2 in water to give the corresponding coupling products 3 in up to 98% isolated yield (25 examples). In the reaction of 4-bromobenzaldehyde with phenylboronic acid, the catalyst was recovered by filtration over a Teflon membrane (0.2 μm pore size) and reused three times with slight loss of its catalytic activity (2nd reuse: 3 h, 86% isolated yield).

A Self-Supported Palladium-Bipyridyl Catalyst for the Suzuki-Miyaura Coupling in Water

A self-supported palladium catalyst (PdCl 2 BPy-Cu) was prepared via construction of a metal-organic framework (MOF) of a bipyridyl-palladium complex bearing carboxylic groups and a copper(II) linker. PdCl 2 BPy-Cu efficiently catalyzed the Suzuki-Miyaura coupling of phenyl halides with arylboronic acids in water under atmospheric conditions to afford the corresponding biaryl products in high yield. The catalyst was reused four times without loss of catalytic activity.

Asymmetric Suzuki-Miyaura Coupling in Water Using a Chiral Polymeric Pd Catalyst

Asymmetric Suzuki-Miyaura coupling in water with a novel recyclable palladium complex of a polymer-supported chiral imidazo­indole phosphine ligand was described. Thus, PS-PEG-supported imidazoindole dicyclohexyl­phosphine (PS-PEG-L*, 7) was prepared from PS-PEG-NH2 and compound 6. The reaction of 2-methyl-1-iodonaphthalene with 2-methylnaphthyl boronic acid was catalyzed by the amphiphilic polymeric PS-PEG-L*-Pd complex to give 2,2′-dimethyl-1,1′-binaphthyl in 95% yield with 94% ee (S). The catalyst PS-PEG-L*-Pd was recovered readily and reused four times with little loss of its catalytic activity and stereoselectivity.

Palladium-Catalyzed Asymmetric Suzuki-Miyaura Coupling in Water

The authors reported an asymmetric Suzuki-Miyaura coupling in water with a recyclable palladium complex of a chiral imidazoindole phosphine ligand supported on an amphiphilic PS-PEG resin. The cross-coupled products were obtained in high enantioselectivities and high yields. The catalyst was readily recovered and reused four times without significant loss of catalytic activity and stereoselectivity.