Suzuki-Miyaura Cross-coupling Reaction Research Articles

Facile Synthesis of 5-Bromo-N-Alkylthiophene-2-Sulfonamides and Its Activities Against Clinically Isolated New Delhi Metallo-β-Lactamase Producing Klebsiella pneumoniae ST147.

New Delhi Metallo-β-lactamase producing Klebsiella pneumoniae (NDM-1-KP) sequence type (ST) 147 poses a significant threat in clinical settings due to its evolution into two distinct directions: hypervirulence and carbapenem resistance. Hypervirulence results from a range of virulence factors, while carbapenem resistance stems from complex biological mechanisms. The NDM-1-KP ST147 clone has emerged as a recent addition to the family of successful clones within the species. In this study, we successfully synthesized 5-bromo-N-alkylthiophene-2-sulfonamides (3a-c) by reacting 5-bromothiophene-2-sulfonamide (1) with various alkyl bromides (2) using LiH. We also synthesized a series of compounds (4a-g) from compound (3b) using the Suzuki-Miyaura cross-coupling reaction with fair to good yields (56-72%). Further, we screened the synthesized molecules against clinically isolated New Delhi Metallo-β-lactamase producing Klebsiella pneumoniae ST147. Subsequently, we conducted in-silico tests on compound 3b against a protein extracted from NDM-KP ST147 with PDB ID: 5N5I. The compound (3b) with favourable drug candidate status, MIC of 0.39 μg/mL, and MBC of 0.78 μg/mL. This low molecular weight compound exhibited the highest potency against the resistant bacterial strains. The in-silico tests revealed that the compound 3b against a protein extracted from NDM-KP ST147 with PDB ID: 5N5I demonstrated H-bond and hydrophobic interactions. The 5-bromo-N-alkylthiophene-2-sulfonamides displayed antibacterial efficacy against New Delhi Metallo-β-lactamase producing Klebsiella pneumoniae ST147. After the in-vivo trial, this substance might offer an alternative therapeutic option.

Synthesis and study of antibiofilm and antivirulence properties of flavonol analogues generated by palladium catalyzed ligand free Suzuki-Miyaura coupling against Pseudomonas aeruginosa PAO1.

The Suzuki-Miyaura coupling is one of the ubiquitous method for the carbon-carbon bond-forming reactions in organic chemistry. Its popularity is due to its ability to undergo extensive coupling reactions to generate a broad range of biaryl motifs in a straightforward manner displaying a high level of functional group tolerance. A convenient and efficient synthetic route to arylate different substituted flavonols through the Suzuki-Miyaura cross-coupling reaction has been explained in this study. The arylated products were acquired by the coupling of a variety of aryl boronic acids with flavonols under Pd(OAc)2 catalyzed reaction conditions in a ligand-free reaction strategy. Subsequently, the antibiofilm and antivirulence properties of the arylated flavonols against Pseudomonas aeruginosa PAO1 were studied thoroughly. The best ligands for quorum sensing proteins LasR, RhlR, and PqsR were identified using molecular docking study. These best fitting ligands were then studied for their impact on gene expression level of P. aeruginosa by RT-PCR towards quorum sensing genes lasB, rhlA, and pqsE. The downregulation in the gene expression with the effect of synthesized flavonols endorse the antibiofilm efficiency of the compounds.

Rational design of galactopyranoside-substituted N-heterocyclic carbene palladium(ii) complexes. Stable and efficient catalyst for C-C coupling in aqueous media.

Following a rational design, three novel palladium(ii) complexes bearing galactopyranoside-based N-heterocyclic carbene ligands have been synthesized via transmetalation of the corresponding Ag(i) complexes. Palladium(ii) complexes have been characterized by NMR, FT-IR and elemental analysis. Catalytic studies, using the Stille and Suzuki-Miyaura cross-coupling reactions as model C-C coupling, reveal that the complexes are active and reusable. The best results in terms of TON values were achieved in aqueous medium using either the in situ deacetylation of the catalyst or the previously deacetylated catalyst. The catalytic condition using in situ deacetylation was more efficient because it avoids an additional deprotection step.

Synthesis of fluoroalkenes and fluoroenynes via cross-coupling reactions using novel multihalogenated vinyl ethers.

In this study, we develop the synthesis methods of fluoroalkenes and fluoroenynes via Suzuki-Miyaura and Sonogashira cross-coupling reactions using novel multihalogenated fluorovinyl ethers, which are easily prepared from the reaction between phenols and 2-bromo-2-chloro-1,1,1-trifluoroethane (halothane). These reactions make use of the unique structure of multihalogenated fluorovinyl ethers, which contains a reactive bromine atom, to afford a series of fluoroalkenes and fluoroenynes in moderate to high yields.

Suzuki–Miyaura cross-coupling reaction catalyzed by [R3Si–IPr]Pd complexes: a computational study

The cross-coupling reaction of chlorobenzene and phenylboronic acid, catalyzed by the [R3Si–IPr]Pd0 species (generated upon activation of {[R3Si–IPr]Pd(173-allyl)Cl} pre-catalyst complexes) in the presence of hydroxide ion as a base, was studied in details by the quantum chemical calculations. Each step of the whole process, including pre- catalyst activation, oxidative addition, transmetalation and reductive elimination, were computationally probed to locate reaction intermediates and transition states along the reaction coordinate. Accordingly, transmetalation was found to be a limiting step of the catalytic cycle (involving oxidative addition, transmetalation and reductive elimination), whereas pre-catalyst activation was revealed as a limiting step of the whole catalytic process.

A novel magnetic nanoparticle as an efficient and recyclable heterogeneous catalyst for the Suzuki cross-coupling reaction

A novel magnetically recyclable heterogeneous palladium catalyst Fe3O4@FSM@Pd was constructed and characterized, which is highly efficient and reusable for the Suzuki–Miyaura cross-coupling reaction.

Magnetic Pd–Fe nanoparticles for sustainable Suzuki–Miyaura cross-coupling reactions

The development of palladium-catalyzed cross-coupling reactions has been revolutionized by bimetallic co-catalysis and magnetic separation techniques, which address the dual challenges of reducing the reliance on palladium (Pd) and advancing sustainable chemistry practices.

Combining Hammett σ constants for Δ-machine learning and catalyst discovery

We present a simple and fast linear model for discovering organometallic catalysts for the Suzuki–Miyaura cross-coupling reaction, using a combinatorial approach.

Unexpectedly superior efficiency of chloride-directed double Suzuki–Miyaura cross-coupling reactions to bromide-directed reactions for the synthesis of sterically hindered 2,7-diaryl fluorenes

Sterically hindered 2,7-diaryl fluorenes have been efficiently synthesized via double Suzuki–Miyaura cross-coupling reactions of challenging 2,7-dichlorofluorene with multiple di-ortho-substituted arylboronic acids using the NHC–Pd catalyst INPd.

Expression of concern: Palladium nanoparticles supported on 1,3-dicyclohexylguanidine functionalized mesoporous silica SBA-15 as highly active and reusable catalyst for the Suzuki–Miyaura cross-coupling reaction

Expression of concern for ‘Palladium nanoparticles supported on 1,3-dicyclohexylguanidine functionalized mesoporous silica SBA-15 as highly active and reusable catalyst for the Suzuki–Miyaura cross-coupling reaction’ by Hojat Veisi et al., RSC Adv., 2015, 5, 20098–20107, https://doi.org/10.1039/C4RA14668A.

Electrochemical removal of toxic metals from reaction media following catalysis.

Following Ni-catalysed Suzuki-Miyaura cross coupling reactions, Ni is electrochemically removed on to the cathode, offering potential for recovery and reuse. The electrochemical recovery method, in combination with an analytical method developed for accurate quantification by HPLC, is expected to be broadly applicable to metal recovery following catalysis.

Inherently chiral nor-heteracalixarenes: design and synthesis via enantioselective intramolecular Suzuki-Miyaura reaction.

There has been a recent upsurge in research aimed at synthesizing inherently chiral molecules devoid of point, axial, planar and helical chiralities. We present herein our design and enantioselective synthesis of a series of inherently chiral macrocycles. These compounds, termed nor-heteracalixaromatics, feature a biaryl bond that replaces one of the aryl-heteroatom-aryl linkages found in classic heteracalix[4]aromatics. Macrocyclization of linear achiral substrates via an intramolecular Suzuki-Miyaura cross-coupling reaction affords the 15-membered cyclophane without any chiral elements in high yields and enantioselectivities. Notably, the formation of the aryl-aryl bond does not induce axial chirality at the biaryl linkage. Instead, it restricts the free rotation of an aromatic ring located four bonds away, leading to the inherent chirality of the macrocycle. The intriguing chiroptical properties of these compounds made them promising platform for the development of CPL emitters.

Palladium recovery from acidic solution with phenanthroline-based covalent organic polymers as adsorbents for efficient heterogeneous catalysis

Highly efficient and selective recovery of Pd(II) from high-level liquid waste (HLLW) was realized by new phenanthroline-based organic polymers for subsequent heterogeneous catalysis of Suzuki-Miyaura cross-coupling reactions.

Synthesis of NiII porphyrin-NiII 5,15-diazaporphyrin hybrid tapes.

NiII porphyrin (P) and NiII 5,15-diazaporphyrin (DAP) hybrid tapes were synthesized by Suzuki-Miyaura cross-coupling reactions of meso- or β-borylated P with β-brominated DAP followed by intramolecular oxidative fusion reactions. Meso-β doubly linked hybrid tapes were synthesized by oxidation of singly linked precursors with DDQ-FeCl3. Synthesis of triply linked hybrid tapes was achieved by oxidation with DDQ-FeCl3-AgOTf with suppression of peripheral β-chlorination. In these tapes, DAP segments were present as a 20π-electronic unit, but their local antiaromatic contribution was trivial. Remarkably, these hybrid tapes were stable and exhibited extremely enhanced absorption bands in the NIR region and multiple reversible redox waves. A pentameric hybrid tape showed a remarkably sharp and red-shifted band at 1168 nm with ε = 5.75 × 105 M-1 cm-1. Singly linked P-DAP dyads were oxidized with DDQ-FeCl3 to give stable radicals, which were oxidized further to afford dimeric hybrid tapes possessing a nitrogen atom at the peripheral-side meso-position.

Selective recognition and enrichment of C70 over C60 using an anthracene-based nanotube.

Selective recognition and enrichment of fullerenes (e.g., C60 and C70) remains challenging due to the same diameter and geometrical similarity. Herein, we report a hexagonal anthracene-based nanotube (1) through a one-pot Suzuki-Miyaura cross-coupling reaction. With anthracene-based side walls and pyridine linkers, 1 features a nano-scale tubular cavity measuring 1.2 nm in diameter and 0.9 nm in depth, along with pH-responsive properties. Interestingly, the electron-rich 1 shows high binding affinity (K a ≈ 106 M-1) and selectivity (K s ≈ 140) to C70 over C60 in toluene, resulting from their different contribution of π-π interactions with the host. The protonation of 1 simultaneously alters the electronic properties within the nanotube, resulting in the release of the fullerene guests. Lastly, the selective recognition and pH stimuli-responsive properties of the nanotube have been utilized to enrich C70 from its low-content mixtures of fullerenes in chloroform.

Palladium-catalyzed Suzuki-Miyaura cross-coupling of carboxylic-phosphoric anhydrides via C-O bond cleavage.

A robust palladium-catalyzed Suzuki-Miyaura reaction of carboxylic-phosphoric anhydrides via highly selective C(O)-O bond cleavage under inorganic base-free conditions has been reported. Carboxylic-phosphoric anhydrides, generated through activating carboxylic acids using phosphates by esterification or direct dehydrogenative reaction with phosphites, have been employed as highly reactive electrophiles for Suzuki-Miyaura cross-coupling reactions. Broad substrate scope and excellent functional group tolerance have been demonstrated to be a general and practical approach for the synthesis of highly valuable ketones.

Retraction: Synthesis and characterization of a supported Pd complex on volcanic pumice laminates textured by cellulose for facilitating Suzuki-Miyaura cross-coupling reactions.

[This retracts the article DOI: 10.1039/D0RA04521G.].

Pd-Catalyzed Suzuki-Miyaura Cross-Coupling Reaction in Glycerol Using KOH as Base and Glycerol-Triethanolamine Deep Eutectic Solvent under Inorganic Base‑Free Conditions

Glycerol and glycerol-triethanolamine deep eutectic solvent are both environmentally benign, cost-effective, and practical solvents for the Pd-catalyzed Suzuki-Miyaura cross-coupling of aryl halides with arylboronic acids. Utilizing KOH as base, the reaction in glycerol proceeded smoothly with low catalyst loadings (up to 0.5 mol% of PdCl2(PPh3)2) providing excellent yields (up to 99%) of the cross-coupling products, which can be readily extracted with hexane. However, the recyclability of the glycerol medium containing the catalyst is limited to a few cycles. Furthermore, it was explored the use of chlorodiphenylphosphine as a pre-ligand. Although glycerol phosphinite was not generated in situ, PPh2Cl proved to be an excellent pre-ligand, yielding the coupling product with a 98% yield. Compared to glycerol, glycerol-triethanolamine deep eutectic solvent (TEOA:G DES) proves to be a superior solvent for the cross-coupling reaction. In addition, the presence of amine group in the solvent allowed to obtain an inorganic base-free cross-coupling protocol. Aryl bromides and aryl boronic acids containing both electron releasing and attracting functional groups can be coupled without requiring the addition of any further base, affording the biphenyl products in moderate to good yields. The cross-coupling products can be easily isolated by extraction with hexane. Moreover, we observed the formation of triethanolamine phenylboronate during the reaction. The triethanolamine boronate was subsequently synthesized through the condensation of phenylboronic acid with triethanolamine and fully characterized. 11B nuclear magnetic resonance (NMR) spectroscopy confirmed the coordination of the nitrogen to the boron atom of the triethanolamine boronate.

Synthesis of Functionalized Hexahydrocarbazoles by Beckmann Elimination and Nucleophile-Intercepted Beckmann Fragmentation.

The Beckmann elimination and nucleophile-intercepted Beckmann fragmentation (NuBFr) of oximes starting from regioisomeric indolinyl bicyclic ketones lead to products that are subjected to further synthetic manipulations and ultimately result in the stereospecific formation of densely functionalized hexahydrocarbazoles. The Pd-catalyzed Suzuki-Miyaura cross-coupling reaction of a key alkenyl bromide intermediate with various boronic acids gives arylated products.

Synthesis of Trifluoromethylated Pyrimido[1,2-b]indazole Derivatives through the Cyclocondensation of 3-Aminoindazoles with Ketoester and Their Functionalization via Suzuki-Miyaura Cross-Coupling and SNAr Reactions.

A new series of trifluoromethylated pyrimido[1,2-b]indazol-4(1H)-one derivatives was synthesized with good to excellent yields through a simple condensation of 3-aminoindazole derivatives with ethyl 4,4,4-trifluoro 3-oxobutanoate. The functionalization of the corresponding chlorinated fused tricyclic scaffolds via Suzuki-Miyaura and aromatic nucleophilic substitution reactions led to the synthesis of highly diverse trifluoromethylated pyrimido[1,2-b]indazole derivatives with good yields.