Suzuki Miyaura Research Articles

NiPd Nanoparticles on Nanoporous Carbon Embedded in Graphitic Carbon Nitride for Transfer Hydrogenation and Suzuki–Miyaura Coupling Reactions

NiPd Nanoparticles on Nanoporous Carbon Embedded in Graphitic Carbon Nitride for Transfer Hydrogenation and Suzuki–Miyaura Coupling Reactions

Roles of Divinylbenzene Co‐Cross‐Linker in a Threefold Cross‐Linked Polystyrene–Phosphine Hybrid Monolith: Impact of Cross‐linking Degree on Catalytic Performance

AbstractContinuous‐flow organic transformations using immobilized catalysts are crucial for green and sustainable chemistry. Cross‐linked polymer ligands offer high stability, ease of recovery through filtration, and thus enhance performance in continuous‐flow reactions via transition‐metal catalysis. Additionally, the cross‐linking structure of the polymer support creates a unique reaction platform that controls the coordination behavior of the supported ligands and stabilizes the metal catalysts. However, insights into the material‐based design for preparing highly active and durable immobilized metal catalysts are still limited. In this report, we propose a straightforward approach to boost both selective mono‐coordination and effective stabilization of metal complexes. We developed threefold cross‐linked polystyrene‐triphenylphosphine hybrid monoliths with cross‐linking structures adjusted by varying the content of divinylbenzene as co‐cross‐linker. The coordination behaviors and metal‐support interactions of these monoliths were evaluated, highlighting the importance of co‐cross‐linker content in site‐isolating phosphine units and stabilizing metal centers via arene‐metal interactions on the polystyrene network. By optimizing the cross‐linking structure, the monolith catalysts demonstrated exceptionally high catalytic activity and durability in Pd‐catalyzed C−Cl transformations, such as Suzuki–Miyaura cross‐couplings and Buchwald‐Hartwig aminations in continuous flow. This underscores the utility of our monolith system in challenging transition‐metal catalysis.

Facile Synthesis of (S)‐2‐Aryl‐N‐(1‐phenylethylisonicotinamides) Derivatives via SMC Reaction: Their Thermodynamic and Spectroscopic Features via DFT Approach

AbstractIn this study, 2‐bromoisonicotinic acid and (S)‐1‐phenylethaneamine were reacted in the presence of pyridine and TiCl4 to produce 2‐bromo‐N‐(1‐phenylethyl)isonicotinamide (3). The derivatives (5a–f) of (S)‐2‐bromo‐N‐(1‐phenylethyl)isonicotinamide were then created by a Suzuki–Miyaura cross‐coupling process catalyzed by palladium (0) and K3PO4 as a base. The reactivity and electronic features of the compounds were investigated using DFT molecular electrostatic potential investigations, reactivity descriptors, and frontier molecular orbital analysis.

Functionalization of thiazolo[5,4-c]isoquinolines through Suzuki–Miyaura coupling

Functionalization of thiazolo[5,4-c]isoquinolines through Suzuki–Miyaura coupling

Synthesis, Characterization, and Catalysis of Planar Chiral Ferrocene‐based N‐Heterocyclic Carbene Ligands and Its Metal Complexes

AbstractThis study presents the development of a novel planar chiral ferrocene‐based NHC ligand and its corresponding metal complexes. The key unit of the imidazolium backbone, planar chiral ortho‐isopropyl ferrocenyl amine, was synthesized starting from (S)‐Ugi's amine. Imidazolium was obtained through the sequential condensation of glyoxal with ferrocenyl amine, followed by the ring‐closure of 1,3‐diferrocenyldiimine with chloromethylethyl ether. Chiral imidazolylidene NHC (IFcPr) metal complexes were prepared by treating imidazolium with silver oxide or base followed by transmetalation with appropriate metal salts. The steric and electronic properties of the IFcPr ligand were assessed using %Vbur and TEP, respectively. These assessments indicated that the ligand was as bulky as the adamantyl NHC ligand and exhibited strong donor ability similar to that of a triazolylidene NHC ligand. The catalytic performance of the copper and palladium complexes was evaluated in the asymmetric borylation of ethyl cinnamate and Suzuki–Miyaura coupling reactions, respectively. The IFcPr−Cu complex catalyzed the borylation of ethyl cinnamate with bis(pinacolato) diboron, followed by oxidation to yield the hydroxy ester with 58 % yield and 30 % ee. In contrast, the IFcPr−Pd‐PEPPSI complex provided the axial chiral binaphthyl compound with 59 % yield and 51 % ee at a low catalyst loading (0.1 mol %, TON=590).

Palladium immobilized on functionalized halloysite: A robust catalyst for ligand free Suzuki–Miyaura cross coupling and synthesis of pyrano[2,3-c]pyrazole motifs via four component cascade reaction and their in-silico antitubercular screening

This research introduces a novel organically functionalized halloysite-supported palladium catalyst, HMF-EDA-TMS@HAL-Pd(II) that was synthesized and thoroughly characterized using various analytical techniques like HR-TEM, FEG-SEM, EDX, XPS, FTIR, XRD, TGA, ICP-AES, EXAFS and DFT studies. The catalyst exhibited exceptional performance in Suzuki–Miyaura cross coupling reactions, demonstrating high efficiency and reusability up to seven cycles in aqueous ethanol medium. Motivated by its promising catalytic activity, we extended our investigation to explore its applicability in the synthesis of pyrano[2,3-c]pyrazole motifs via a four-component cascade reaction affording the desired products in good to excellent yields with broad substrate scope under green reaction conditions. In-silico antitubercular screening of pyrano[2,3-c]pyrazole motifs against DprE1 enzyme have shown promising results with inhibition constants ranging between 0.030 and 0.1 μM for compounds 5b, 5k and 5 l. This protocol has the advantages of wide substrate scope, high yield, excellent functional group tolerance, high efficiency and environmental benign procedure. These findings emphasized the catalyst's versatility and potential in diverse organic transformations, highlighting its importance in advancing sustainable synthetic methodologies.

Facile Fabrication of LaFeO 3 Supported Pd Nanoparticles as Highly Effective Heterogeneous Catalyst for Suzuki–Miyaura Coupling Reaction

Supported Pd catalysts have been widely studied due to their enormous potential as candidates for heterogeneous Suzuki–Miyaura coupling reactions. However, the sintering and low activity of active sites still remain challenges. A vesicle‐shaped LaFeO3‐supported Pd catalyst (I‐Pd/LaFeO3) was successfully fabricated using the impregnation method and tested for the Suzuki–Miyaura coupling reaction. Compared to P‐Pd/LaFeO3 prepared with photo‐deposition and Pd/Al2O3 prepared with impregnation, the I‐Pd/LaFeO3 catalyst exhibits significantly higher catalytic activity, stability, and reusability. The chemical composition and electron states of different Pd‐based catalysts were well studied based on various characterizations and the results indicated that the excellent performance of I‐Pd/LaFeO3 can be attributed to its unique nanostructure and the strong interactions between LaFeO3 and palladium nanoparticles. The impregnation method and the choice of the LaFeO3 support show a great influence on the electronic properties of Pd species, their reducibility, and, consequently, their reaction behavior. This unique LaFeO3 supported Pd catalyst provided an environmentally friendly heterogeneous method for the Suzuki–Miyaura coupling reaction.

Base-free aqueous Suzuki–Miyaura coupling reaction using recoverable bi-functional Pd supported nanocatalyst

A solid base catalyst comprising pyridine-palladium polyorganosiloxane framework was synthesized via a grafting method. The resulting organic–inorganic hybrid palladium nanomaterial was characterized by 13C CP-MAS NMR, 29Si CP-MAS NMR, XRD, EDX, TEM, TGA, and the BET measurements. The hybrid palladium nanomaterial exhibited high catalytic activity for the Suzuki–Miyaura cross-coupling reaction between aryl chlorides and phenylboronic acid under base-free and aerobic conditions. A maximum turnover number (TON) of 3150, with a 0.2 mol% Pd loading and a reaction temperature of 80 °C in aqueous solution. The catalyst demonstrated remarkable stability, maintaining its activity even after six cycles of reuse without significant loss of activity. TEM images showed that the catalyst retained its structure and high-order mesostructure after several uses. ICP-AES also confirmed the absence of palladium contamination in the final products. Leaching test studies further confirmed the true heterogeneous nature of the developed catalytic system.

Post-synthetic sulfonation of resorcinarene-based porous organic polymer for superfast adsorption of diverse organic pollutants

A resorcinarene-based porous organic polymer was synthesized via the Suzuki–Miyaura coupling reaction and then functionalized by chlorosulfonic acid to obtain a sulfonated product named BaPy-SO3H. Characterization results indicate that BaPy-SO3H has porous skeletons, excellent thermal stability, and electronegative surface charges. Remarkably, BaPy-SO3H exhibits superfast rates and reaches adsorption equilibrium within 1 min towards diverse organic pollutants including dyes, herbicides, and antibiotics via electrostatic interactions, π–π interactions, and host–guest effects. Especially for Crystal Violet, Malachite Green, and Paraquat, BaPy-SO3H achieves apparent rate constants for a pseudo-second-order model of 31.24, 31.27, and 30.63 g mg−1 min−1, respectively, which are the highest values among reported adsorbents to the best of our knowledge. Meanwhile, the maximum adsorption capacity of BaPy-SO3H reaches 1850 mg g−1 for Rhodamine B, 2295 mg g−1 for Methyl Blue, 1503 mg g−1 for Crystal Violet, and 1304 mg g−1 for trimethoprim, surpassing most of the adsorbents reported so far. The above results demonstrate the superior adsorption performance of BaPy-SO3H towards diverse organic pollutants and its potential applications in real-water scenarios.

Advancing Base-Metal Catalysis: Developing Nickel Catalysis for the Direct Telescope of Miyaura Borylation and Suzuki–Miyaura Cross-Coupling Reactions

Advancing Base-Metal Catalysis: Developing Nickel Catalysis for the Direct Telescope of Miyaura Borylation and Suzuki–Miyaura Cross-Coupling Reactions

Efficient and Direct Route to 5-Iodo-4H-Quinoxalines via Copper-Catalyzed Double C–N Arylations of 1,2,3-Triiodoarenes: Potential Application towards 5-Substituted 4H-Quinoxalines

AbstractA simple, direct, and regioselective protocol to substituted 5-iodo-4H-quinoxalines through double C–N arylations of 1,2,3-triiodobenzenes and 1,2-diamines is reported. Remarkably, the N-arylation couplings proceed unimolecularly at the vicinal positions, the most active and less hindered positions. This process tolerates a wide range of aromatic substrates. The reactions of electron-deficient 1,2,3-triiodoarene systems and DMEDA under the optimized conditions provided the highest isolated yields. The chemical transformation of the target compound, which serves as a valuable precursor in synthesis, was successfully demonstrated in the Suzuki–Miyaura reaction, giving the desired coupling derivatives with excellent isolated yields. This article describes a method for the first and unprecedented synthesis of 5-iodo-4H-quinoxalines that is regioselective, scalable, and provides useful derivatives for other chemical reactions

Synthetic Routes to 2-aryl-1H-pyrrolo[2,3-b]pyridin-4-amines: Cross-Coupling and Challenges in SEM-Deprotection

7-Azaindoles are compounds of considerable medicinal interest. During development of the structure–activity relationship for inhibitors of the colony stimulated factor 1 receptor tyrosine kinase (CSF1R), a specific 2-aryl-1H-pyrrolo[2,3-b]pyridin-4-amine was needed. Two different synthetic strategies were evaluated, in which the order of the key C-C and C-N cross-coupling steps differed. The best route relied on a chemoselective Suzuki–Miyaura cross-coupling at C-2 on a 2-iodo-4-chloropyrrolopyridine intermediate, and subsequently a Buchwald–Hartwig amination with a secondary amine at C-4. Masking of hydroxyl and pyrroles proved essential to succeed with the latter transformation. The final trimethylsilylethoxymethyl (SEM) deprotection step was challenging, as release of formaldehyde gave rise to different side products, most interestingly a tricyclic eight-membered 7-azaindole. The target 2-aryl-1H-pyrrolo[2,3-b]pyridin-4-amine (compound 3c) proved to be 20-fold less potent than the reference inhibitor, confirming the importance of the N-3 in the pyrrolopyrimidine parent compound for efficient CSF1R inhibition.

Suzuki-Miyaura coupling reaction: Blue-yellow emitting AIE active dyes for organic electronics

A series of eight novel donor‒acceptor (D─A) based 2,3-di(thiophen-2-yl)quinoxaline derivatives 2–9 were prepared by modulating donor species on quinoxaline core with Palladium catalyzed Suzuki–Miyaura ‘C–C bond’ coupling reaction. The synthesized molecules were fully characterized and studied for impact of D–A interaction on opto-electrochemical properties. Absorption spectra of 2–9 display intramolecular charge transfer (ICT) transitions in the range of 388–414 nm. Dyes shows positive solvatochromism and emit in blue‒yellow region with emission maxima 444−550 nm on excitation at their respective ICT maxima in toluene, chloroform, DCM, DMSO and neat solid film. Further, solid state emission was studied for aggregation‒induced emission (AIE) effect in THF–water system due to the nanoparticles formation, as confirmed by FEG‒SEM technique. The HOMO and LUMO energy level for compounds 2–9 were measured by cyclic voltammetry and found in the range of −5.15 to −5.94 eV and −2.81 to −3.39 eV. Theoretical studies of molecules were also carried out by using DFT and TD‒DFT calculations. The comparable HOMO and LUMO energy levels with reported ambipolar materials and efficient solid-state emission make synthesized compounds potential candidate for solid state emissive, ambipolar charge transporting materials in organic electronics.

Concise and Modular Chemoenzymatic Total Synthesis of Bisbenzylisoquinoline Alkaloids

The bisbenzylisoquinoline alkaloids (bisBIAs) have attracted tremendous attention from the synthetic community due to their diverse and intriguing biological activities. Herein, we report the convergent and modular chemoenzymatic syntheses of eight bisBIAs bearing various substitutes and linkages in 5‐7 steps. The gram‐scale synthesis of various well‐designed enantiopure benzylisoquinoline monomers was accomplished via an enzymatic stereoselective Pictet–Spengler reaction, followed by regioselective enzymatic methylation or chemical functionalizations in a sequential one‐pot process. A modified intermolecular copper‐mediated Ullmann coupling enabled the concise and efficient total synthesis of five different linear bisBIAs with either head‐to‐tail or tail‐to‐tail linkage. A biomimetic oxidative phenol dimerization selectively formed the sterically hindered, electron‐rich diaryl ether bond, and subsequent intramolecular Suzuki–Miyaura domino reaction or Ullmann coupling facilitated the first enantioselective total synthesis of three macrocyclic bisBIAs, including ent‐isogranjine, tetrandrine and O‐methylrepandine. This study highlights the great potential of chemoenzymatic strategies in the total synthesis of diverse bisBIAs and paves the way to further explore the biological functions of these natural products.

Arylation of 2‐Chloro‐3‐(4,6‐Diaryl‐1,3,5‐Triazin‐2‐yl) Quinolines: Formal Synthesis of 3‐(4,6‐Diaryl‐1,3,5‐Triazin‐2‐yl)‐2‐Substituted Quinolines by Suzuki–Miyaura Reaction

ABSTRACTWe have described herein a simple and formal two‐step synthesis of 3‐(4,6‐diaryl‐1,3,5‐triazin‐2‐yl)‐2‐aryl quinolines from 2‐chloro‐3‐(4,6‐diaryl‐1,3,5‐triazin‐2‐yl) quinolines and boronic acids under the Suzuki–Miyaura conditions. This protocol provides the C‐2 arylation of 2‐chloro‐3‐(4,6‐diaryl‐1,3,5‐triazin‐2‐yl) quinolines under the mild reaction conditions. These newly formed chemo‐types may be useful in drug discovery programs or in material chemistry.

Light‐Enhanced Suzuki–Miyaura Crosscoupling Reaction by Polyoxopalladates Clusters: Doping Effect

Atomic precise clusters play a pivotal role in elucidating catalytic mechanisms. Emerging well‐defined noble metal oxygen clusters, such as polyoxopalladates (POPs), present promising prospects as ideal model catalysts for comprehensively understanding the molecular mechanisms underlying noble metal‐based catalysis. Herein, modified SBA‐15 serves as a substrate for loading three distinct POP clusters, thus forming heterogeneous catalysts for the Suzuki–Miyaura crosscoupling reaction. It is revealed that the copper‐doped cluster shows better performance than the Fe‐ and Co‐doped clusters due to the relatively high electronegativity of copper. Interestingly, all catalysts demonstrate enhanced performance under light illumination. density functional theory calculation suggests that an electron transfer from the bridging ligands to the Pd atoms takes place under illumination, which facilitates the reactions.

Nanoparticles of PdAu Alloys on BiOBr Nanosheets for Highly Efficient Photocatalytic Suzuki–Miyaura Reactions

Nanoparticles of PdAu Alloys on BiOBr Nanosheets for Highly Efficient Photocatalytic Suzuki–Miyaura Reactions

Expanding the Horizons of Suzuki Reactions: Pd‐PEPPSI–Mediated Traditional and Decarbonylative Couplings With Diverse Assure Analogues

ABSTRACTWe have developed a highly efficient, ligand‐free Suzuki–Miyaura cross‐coupling protocol employing our lab‐prepared air and moisture‐stable Pd‐PEPPSI catalysts. The reaction of ethyl 2‐{4‐[(6‐chloroquinoxalin‐2‐yl)oxy]phenoxy}propionate (Assure) with various boronic acids afforded both traditional and decarbonylative coupling products in high yields. The catalyst's steric influence was assessed computationally using %Vbur calculations. The decarbonylative coupling pathway proved more efficient than the traditional Suzuki–Miyaura coupling under these conditions. Additionally, regioselectivity studies have been conducted on a variety of Assure analogues. This method excels in efficiency, requiring minimal catalyst, moderate temperatures, and rapid reaction completion.

Thianthrenium ions pair-up for Suzuki–Miyaura reactions

Thianthrenium ions pair-up for Suzuki–Miyaura reactions

Facile synthesis, SC-XRD, spectroscopic characterization & key electronic properties of nicotinaldehyde based scaffolds

Currently, pyridine based derivatives (TFMPN, BPN, and APN) have been synthesized using the Suzuki Miyaura coupling reaction and their structural confirmation was ensured by various spectroscopic techniques like UV–Visible, NMR (1H and 13C), and single crystal X-ray diffraction (SC-XRD) studies. After structural elucidation the key electronic properties of the synthesized derivatives were investigated through DFT/TD-DFT approaches at the M06/6–31 G (d, p) functional. The FMOs analysis showed effective charge transmission from HOMO towards LUMO, additionally reinforced by TDM and DOS analyses. Global reactivity parameters (GRPs) verified high softness along with substantial reactivity in TFMPN, BPN, and APN. Moreover, the low values of binding energy (Eb = 1.022–1.778 eV) demonstrate a higher exciton dissociation rate along with better hole movement. Among the chromophores listed above, BPN is regarded as the best due to its lowest energy gap (4.628 eV), maximum absorption maxima (344.429 nm), and softness (0.216 eV) characteristics therefore, it exhibits effective key electronic properties among all entitled chromophores.