Fluorapatite‐Supported Palladium Catalyst for Suzuki and Heck Coupling Reactions of Haloarenes

A fluorapatite‐supported palladium catalyst (PdFAP) was synthesized by treatment of fluorapatite (prepared by incorporating the basic species fluoride ion into apatite in situ by co‐precipitation) with bis(benzonitrile)palladium(II ) chloride in acetone. The catalyst displayed high catalytic activity for Suzuki coupling of aryl iodides and bromides with boronic acids at room temperature and chloroarenes at 130 °C in the presence of tetrabutylammonium bromide to give biaryls in excellent yields. Heck olefination of chloroarenes was also successfully carried out by this catalyst. PdFAP was recovered quantitatively by simple filtration and reused with consistent activity. PdFAP was well characterized by XRD, FTIR, XPS, ICP‐AES, CO₂ TPD and CHN elemental analysis.     

Homogeneous Catalysis for the Production of Fine Chemicals. Palladium- and Nickel-Catalysed Aromatic Carbon–Carbon Bond Formation

In this article we describe our recent efforts in the area of palladium- and nickel-catalysed aromatic substitution reactions. Main focus is on low cost and low waste production methods. The use of aromatic carboxylic anhydrides in the Heck reaction leads to a waste-free protocol. In addition these reactions are easy to work up as no ligands or bases are used. For Heck reactions where substrates or products do not tolerate high temperatures we found that use of a bulky phosphoramidite (13b) as ligand for palladium leads to a very fast reaction at low temperatures. Recycle of palladium in ligand-free Heck and Suzuki reactions is easily accomplished by treating the palladium black that precipitates at the end of the reaction on a carrier material with a small excess of I₂ prior to its re-use in the next run. Use of aryl chlorides in the palladium- and nickel-catalysed formation of biaryls can be accomplished by using the nickel-catalysed coupling with arylzinc chlorides. Better still, it was possible to make use of the arylgrignard and use a catalytic amount of ZnCl₂. Whereas the strength of these aromatic substitution reactions lies in their broad tolerance of functional groups, one exception was the Sonogashira reaction on 3-bromoaniline. The problem was solved by making use of in situ catalytic protection of the NH₂ group with benzaldehyde.     

A novel thermo and pH-double sensitive hydrogel immobilized Pd catalyst for Heck and Suzuki reactions in aqueous media

A novel Hydrogel (1) was prepared from N-isopropylacrylamide, 4-vinylpyridine and potassium acrylate by free radical cross-linking polymerization. Hydrogel (1) showed both thermosensitivity and pH-sensitivity, and exhibited high swelling capacity in water. Because Hydrogel (1) has porous structure in its network and good loading performance with Pd²⁺, it was used as “microreactor” for immobilization of metal nanoparticles. We chose Heck and Suzuki reaction of aryl halides in water as test reaction to probe the catalytic activity of such Hydrogel (1) supported palladium catalyst. As a result, the Hydrogel (1)-Pd (II) catalyst exhibited good catalytic activity in both Heck and Suzuki reactions. Moreover, the Hydrogel (1)-Pd (II) catalyst was easily recovered and recycled. The reuse experiments showed that it was recycled six times without obviously losing of catalytic activity.     

A facile preparation of palladium Schiff base complex supported into MCM-41 mesoporous and its catalytic application in Suzuki and Heck reactions

A simple and efficient method for phosphine-free C–C coupling reactions such as Heck and Suzuki reactions in the presence of pyrrole Schiff base complex of palladium immobilized on mesoporous mesoporous of MCM-41 (Pd-Py-MCM-41) has been reported. The Suzuki reaction was carried out in PEG-400 using phenylboronic acid (PhB(OH)₂). Pd-Py-MCM-41 has been found as a promising catalyst for Heck reaction of butyl acrylate with aryl halides (including Cl, Br and I). The catalyst was characterized by FT-IR, TEM, XRD, SEM, BET and ICP-OES techniques. The protocol proves to be efficient and environmentally benign in terms of high yield, easy of recovery and reusability of catalyst.     

Macrocyclic Palladium(II) Complexes in C?C Coupling Reactions: Efficient Catalysis by Controlled Temporary Release of Active Species

Stabilization of palladium species against agglomeration is essential for reasonable catalytic activity in C C coupling reactions. In contrast to common methods of palladium(0) complex or particle stabilization, a new concept is introduced here: it is demonstrated that a controlled release of palladium from an inactive precatalyst provides stability, too, and leads to high catalytic activity. This paper presents surprising catalytic results for Heck and Suzuki reactions with aryl chlorides and bromides, using three highly stable macrocyclic palladium complexes as catalyst precursors. Three different behaviour patterns for the macrocyclic complexes can be deduced from the evaluation of catalytic activities, UV‐Vis spectroscopy, recycling studies of immobilized complexes, and ligand addition experiments. (i) Palladium tetraphenylporphyrin reversibly releases only extremely low amounts of palladium during the reactions, and low coupling activities are observed. (ii) Release of palladium from its phthalocyanine complex is irreversible; cumulative release of palladium into the reaction mixtures leads to high catalytic activity. (iii) Extraordinary results were obtained with a Robson‐type complex of palladium, which reversibly releases effectual amounts of palladium into solution under reaction conditions. This controlled release prevents the formation of inactive palladium agglomerates under harsh conditions and leads to high catalytic performances. Even strongly deactivated electron‐rich aryl chlorides (4‐chloroanisole) can be completely and selectively converted by the in situ formed anionic palladium halide complexes; the addition of typical stabilizing additives (TBAB) was found to be unnecessary. The bimetallic palladium complex is regenerated at the end of the reaction. These results contribute to the current understanding of the active species in C C coupling reactions of Heck and Suzuki types.     

Suzuki‐ and Heck‐Type Cross‐Coupling with Palladium Nanoparticles Immobilized on Spherical Polyelectrolyte Brushes

We report on a systematic study of the use of palladium nanoparticles immobilized on spherical polyelectrolyte brushes – Pd@SPB – for Heck‐ and Suzuki‐type coupling reactions. The spherical polyelectrolyte brush particles serving as carriers for the palladium nanoparticles consist of a solid polystyrene core with a radius of 46 nm onto which long chains of cationic polyelectrolytes are grafted. The palladium nanoparticles have directly been generated within this brush layer and the stabilization of the nanoparticles is effected by the colloidal carriers, no further surface stabilization is necessary. We demonstrate that these composite particles present robust catalysts for the Heck‐ and Suzuki‐type coupling reactions. This was shown by carrying out the Suzuki‐ and Heck‐type coupling reactions at relatively low temperatures (Suzuki reaction: 50 °C, Heck reaction: 70 °C). We demonstrate that the catalytic composite particles are not changed by these reaction conditions and retain their full activity for at least four runs. The yields obtained for both reactions are good to excellent. The mild operation conditions of the palladium nanoparticles are traced back to the absence of surface stabilization. Further mechanistic implications are discussed.     

Palladium nanoparticles embedded chitosan/poly(vinyl alcohol) composite nanofibers as an efficient and stable heterogeneous catalyst for Heck reaction

In this study, palladium nanoparticles were successfully embedded into modified chitosan/poly(vinyl alcohol) composite nanofibers (Pd-CS/PVA nanofibers) by electrospinning. Then, the Pd-CS/PVA nanofibers were treated at evaluated temperature to improve its solvent resistance and in situ reduce Pd²⁺ cations into Pd⁰ active species. The incorporated palladium nanoparticles with ultra small mean diameter of 3.73 ± 1.04 nm are evenly distributed inside the Pd-CS/PVA nanofiber. The resulting Pd-CS/PVA nanofiber mat exhibits high catalytic activity for Heck reaction of aromatic iodides with alkenes and can be recycled for 18 times without loss of initial activity. The high catalytic activity and stability of Pd-CS/PVA nanofiber mat can be attributed to the ultra small diameter nanofibers, strong chelating ability of chitosan, and fine embedment of palladium species inside the nanofiber. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48026.     

Palladium Nanoparticles Immobilized on Nano‐Silica Triazine Dendritic Polymer (Pdnp‐nSTDP): An Efficient and Reusable Catalyst for Suzuki–Miyaura Cross‐Coupling and Heck Reactions

A new catalyst based on palladium nanoparticles immobilized on nano‐silica triazine dendritic polymer (Pd_np‐nSTDP) was synthesized and characterized by FT‐IR spectroscopy, thermogravimetric analysis, field emission scanning electron microscopy, energy dispersive X‐ray, transmission electron microscopy and elemental analysis. The size of the palladium nanoparticles was determined to be 3.1±0.5 nm. This catalytic system showed high activity in the Suzuki–Miyaura cross‐coupling of aryl iodides, bromides and chlorides with arylboronic acids and also in the Heck reaction of these aryl halides with styrenes. These reactions were best performed in a dimethylformamide (DMF)/water mixture (1:3) in the presence of only 0.006 mol% and 0.01 mol% of the catalyst, respectively, under conventional conditions and microwave irradiation to afford the desired coupling products in high yields. The Pd_np‐nSTDP was also used as an efficient catalyst for the preparation of a series of star‐ and banana‐shaped compounds with a benzene, pyridine, pyrimidine or 1,3,5‐triazine unit as the central core. Moreover, the catalyst could be recovered easily and reused several times without any considerable loss of its catalytic activity.     

Novel Pd-BTP/SiO2 as an Effective Heterogeneous Catalyst for Heck Reactions

A highly efficient and reusable catalyst, palladium (II) complex supported on functionalized silica, was prepared by anchoring palladium (II) onto 2,6-bis(5,6-dimethyl-1,2,4-triazine-3-yl)pyridine [BTP]-modified mesoporous silica (labeled as Pd-BTP/SiO₂). The catalyst was characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and Brunauer Emmett Teller (BET) analysis. Its catalytic performance was tested for the Heck coupling reactions between aryl halides with acrylic acid or styrene, and good to excellent results (higher conversions 87–96% and yields 66–78%) were obtained. The catalyst system was stable under the reaction conditions and could be successfully reused more than five times without the loss of catalytic activity.     

Development of Efficient and Reusable Diarylphosphinopolystyrene‐Supported Palladium Catalysts for C?C Bond Forming Cross‐Coupling Reactions

Short and versatile syntheses of reusable diarylphosphinopolystyrene‐supported palladium catalysts 3a – j are described. The bis(o‐tolyl)phosphino catalyst 3b is particularly efficient for the Suzuki and Sonogashira cross‐couplings, whereas the bis(m‐tolyl)phosphino catalyst 3c is the most active catalyst for Heck reactions. The couplings are performed under non‐anhydrous reaction conditions and require only low amounts of supported palladium (0.5 mequivs. for Suzuki–Miyaura, 1.0 mequiv. for Sonogashira and 0.5 mequivs. for Heck reactions could be sufficient). Catalysts 3a–j are recovered by filtration and can be reused more than four times with no loss of efficiency.     

Polypyrrole–Palladium Nanocomposite-Coated Latex Particles as a Heterogeneous Catalyst in Water

Abstract  

Polypyrrole–palladium nanocomposite-coated cross-linked polystyrene latex particles (PS/PPy–Pd) showed an excellent catalytic activity for Suzuki and Heck reactions in aqueous media. The PS/PPy–Pd can be recovered easily and quantitatively through the repeated uses with simple filtration and they maintain their high catalytic activities.     

Thiosemicarbazone Salicylaldiminato‐Palladium(II)‐Catalyzed Mizoroki–Heck Reactions

Four tridentate thiosemicarbazone salicylaldiminato‐palladium(II) complexes of the general formula [Pd(saltsc‐R)PPh₃] [saltsc=salicylaldehyde thiosemicarbazone; R=H ( 1 ), 3‐tert‐butyl ( 2 ), 3‐methoxy ( 3 ), 5‐chloro ( 4 )], have been evaluated as catalyst precursors for the Mizoroki–Heck coupling reaction between a variety of electron‐rich and electron‐poor aryl halides and olefins. The palladium complexes (0.1–1 mol% loading) were found to effectively catalyze these reactions with high yields being obtained when aryl iodides and aryl bromides were utilized. The effects of base, catalyst loading, reaction temperature and reaction time on the catalytic activity of the most active complex were also investigated.     

Pd/C embedded crosslinked polystyrene fibers as an efficient catalyst for Heck reactions

Pd/C embedded polystyrene fibers were successfully prepared by electrospinning. The polystyrene molecules were then cross-linked by paraformaldehyde in sulfuric acid to improve the solvent resistance of composite fibers. SEM images conformed the preparation of uniform and smooth composite fibers. FT-IR spectra demonstrated that the polystyrene molecules inside fibers have been sulphonated and crosslinked. Heck reactions were used to evaluate the catalytic performance of these novel composite fibers. The catalysis results show that this composite fiber mat catalyzed Heck reactions could be evidently promoted by using preferred reducing alcohol agent and solvent. Under the optimized reaction conditions, this composite fiber mat could effectively catalyze the Heck reactions of aromatic iodides with n-butyl acrylate to afford the products with satisfied yields. Especially, compared with the particulate Pd/C catalyst, the separation and recycling of this fibrous catalyst from the reaction mixture were significantly improved due to the larger fibrous structure. At last, this fiber catalyst was successfully reused for eight times with little loss of initial catalytic activity, which was even better than the pristine Pd/C catalyst. Hence, embedment of particulate supported metal catalysts inside the crosslinked polystyrene fibers can effectively improve their catalytic performance and handiness.     

Novel Type of Metal-Containing Polyimides for the Heck and Suzuki–Miyaura Cross-Coupling Reactions as Highly Active Catalysts

Novel palladium (II)-containing polyimides with exceptional catalytic properties for the Heck and Suzuki–Miyaura cross-coupling reactions were prepared from Pd(II)--bis(imine) complex and the corresponding dianhyrides. The glass transition temperatures (T _g ) of the polymers ranged from 169 to 241°C. The temperatures at which 10% weight loss occurred in air ranged from 415 to 579°C. Polyimides based on the palladium (II) complex were tested for catalytic activity in the Heck coupling reaction between styrene and several aryl halides and the Suzuki coupling reaction between phenylboronic acid and several aryl halides. The negative effects (e.g., expense, low reaction rates, air-sensitivity) experienced by using phosphines, particularly electron-rich phosphines, as catalysts in large scale applications is overcome by using polymer supported catalysis.     

Suzuki Coupling Reactions in Pure Water Catalyzed by Supported Palladium – Relevance of the Surface Polarity of the Support

Heterogeneous (supported) palladium catalysts like palladium on carbon and a variety of metal oxides have been shown to be highly active for Suzuki coupling reactions in neat water under mild reaction conditions (T=65 °C). It has been demonstrated for the first time that hydrophobic effects of the catalyst surface play an important role for the catalyst activity in water. Catalysts possessing hydrophobic surfaces (e.g., palladium on carbon) show higher activity for Suzuki coupling reactions in water than their hydrophilic counterparts (palladium on metal oxides). Tuning of the surface polarity of metal oxide supports (by silylation) results in higher activity under these conditions. Stronger alkaline conditions (three‐fold excess of base) compensate the effect of hydrophobic supports and result in high activity of the catalysts also with hydrophilic supports. The addition of tetrabutylammonium bromide to generate, activate and stabilize the catalytic species (dissolved palladium complexes) is necessary for the conversion of more demanding substrates. The reaction is considered to be homogeneous taking place near the catalyst surface inside a droplet or layer of the reactant.     

A Reusable Polymer-Anchored Palladium(II) Schiff Base Complex Catalyst for the Suzuki Cross-Coupling,Heck and Cyanation Reactions

A new polymer-anchored Pd(II) complex has been synthesized, characterized and its catalytic activity was investigated for the Suzuki cross-coupling reaction between aryl halides and arylboronic acid in the presence of K₂CO₃ as a base, for Heck olefination of aryl halides with alkenes, and for cyanation reaction of aryl iodides with K₄Fe(CN)₆ in presence of Et₃N as base. The key features of the catalyst include rapid reactions with excellent conversion without the use of phosphine ligands and total stability under the reactions conditions. The catalyst was recovered by simple filtration and reused five-times without significant loss of catalytic activity.     

Ligandless palladium supported on SiO2–TiO2 as effective catalyst for Suzuki reaction

TiO₂–SiO₂ mixed oxides were prepared by the homogeneous precipitation method, and the supports were characterized by XRD, IR and BET. Ligandless palladium supported on SiO₂–TiO₂ was prepared by the deposition–precipitation method and used as recoverable catalyst for Suzuki reactions. The results revealed that the supported catalyst Pd/SiO₂–TiO₂ exhibited excellent catalytic activity for the coupling of aryl bromides with arylboronic acid, and also exhibited moderate catalytic activity for the coupling of aryl chlorides. The catalyst was recycled by simple filtration and reused without further disposal, no significant Pd leaching and loss of catalytic activity was observed except the first reuse.     

Regioselective Palladium(0)‐Catalyzed Cross‐Coupling Reactions and Metal‐Halide Exchange Reactions of Tetrabromothiophene: Optimization,Scope and Limitations

The Suzuki reaction of tetrabromothiophene with arylboronic acids provides a regioselective approach to various 5‐aryl‐2,3,4‐tribromothiophenes, symmetrical 2,5‐diaryl‐3,4‐dibromothiophenes, and tetraarylthiophenes. Unsymmetrical 2,5‐diaryl‐3,4‐dibromothiophenes are prepared by Suzuki reaction of 5‐aryl‐2,3,4‐tribromothiophenes. Tetraarylthiophenes containing two different types of aryl groups are obtained by Suzuki reactions of 2,5‐diaryl‐3,4‐dibromothiophenes. During the optimization of the conditions of each individual reaction, the solvent, the catalyst and the temperature play an important role. In several cases, classical conditions [use of tetrakis(triphenylphosphane)palladium(0), Pd(PPh₃)₄, as the catalyst] gave excellent yields. The yields of those transformations which failed or proceeded sluggishly could be significantly improved by application of a new biarylmonophosphine ligand developed by Buchwald and co‐workers. Regioselective metal‐halide exchange reactions of tetrabromothiophene provide a convenient approach to various 2,5‐disubstituted 3,4‐dibromothiophenes. 5‐Alkyl‐2‐trimethylsilyl‐3,4‐dibromothiophenes could be prepared in one pot by sequential addition of trimethylchlorosilane and alkyl bromides. The reaction of tetrabromothiophene with methyl chloroformate and subsequent Suzuki reactions afforded 3,4‐diaryl‐2,5‐bis(methoxycarbonyl)thiophenes.     

On the Nature of the Active Species in Palladium Catalyzed Mizoroki–Heck and Suzuki–Miyaura Couplings – Homogeneous or Heterogeneous Catalysis,A Critical Review

A wide array of forms of palladium has been utilized as precatalysts for Heck and Suzuki coupling reactions over the last 15 years. Historically, nearly every form of palladium used has been described as the active catalytic species. However, recent research has begun to shed light on the in situ transformations that many palladium precatalysts undergo during and before the catalytic reaction, and there are now many suggestions in the literature that narrow the scope of types of palladium that may be considered true “catalysts” in these coupling reactions. In this work, for each type of precatalyst, the recent literature is summarized and the type(s) of palladium that are proposed to be truly active are enumerated. All forms of palladium, including discrete soluble palladium complexes, solid‐supported metal ligand complexes, supported palladium nano‐ and macroparticles, soluble palladium nanoparticles, soluble ligand‐free palladium, and palladium‐exchanged oxides are considered and reviewed here. A considerable focus is placed on solid precatalysts and on evidence for and against catalysis by solid surfaces vs. soluble species when starting with various precatalysts. The review closes with a critical overview of various control experiments or tests that have been used by authors to assess the homogeneity or heterogeneity of catalyst systems.     

Carboncarbon bond forming reactions: Application of covalently anchored 2,4,6-triallyloxy-1,3,5-triazine (TAT) Pd(II) complex over modified surface of SBA-15 to Heck,Suzuki, Sonogashira and Hiyama cross coupling reactions

A highly active SBA-15-TAT-Pd(II) catalyst was synthesized from organofunctionalized SBA-15 and 2,4,6-triallyloxy-1,3,5-triazine. The catalyst was employed in carrying out Heck, “copper-free” Sonogashira, Suzuki and Hiyama cross coupling reactions. Under the optimized conditions the catalyst displays excellent catalytic activity in delivering the desired products in good to excellent yields. The catalytic system exhibited superior activity regarding the time taken for the completion of reaction, isolation, Pd loading (0.62 mmol%) and yields of products as compared to the earlier reported heterogeneous SBA-15 anchored Pd catalysts. The catalyst could be recycled and reused for five times without any appreciable loss of catalytic activity.