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Review Article
ARTICLE IN PRESS
doi:
10.25259/AJC_611_2025

Recent developments in transition metals supported on functionalized materials for enhancing Suzuki reactions

, , ,
aSchool of Chemical and Environmental Engineering, Anhui Polytechnic University, Wuhu, PR China
bHenan Key Laboratory of Green Chemistry, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Henan Engineering Laboratory of Chemical Pharmaceutical and Biomedical Materials, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, PR China
cKey Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, PR China

*Corresponding authors: E-mail addresses: bijiajun@ahpu.edu.cn (J. Bi), taoli@hust.edu.cn (T. Li)

Received: , Accepted: ,
© 2026 Arabian Journal of Chemistry - Published by Scientific Scholar
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Abstract

The construction of aryl˗aryl, aryl˗heteroaryl or heteroaryl˗heteroaryl linkages via Suzuki coupling reactions is essential and common in industrial applications, which warrants the development of the pharmaceutical drugs, dyes, and agrochemicals fields. In this review, the general mechanism and practical application of Suzuki reactions are briefly described. Importantly, special attention is paid to the C-C coupling activity of supported Pd catalysts based on diverse recently developed materials. Furthermore, the application of the transition metals-based heterogeneous catalysts (Ni, Cu, Fe, Co) in Suzuki reactions was also summarized and compared. It is anticipated that this overview will improve current understanding and motivate further innovation toward the development of highly efficient and low-cost heterogeneous catalysts for Suzuki coupling reactions.

Keywords

Green synthesis
Heterogeneous catalyst
Palladium
Support material
Suzuki reaction

1. Introduction

Suzuki reactions lie at the central core of industrial synthesis of pharmaceutical drugs, dyes, and agrochemicals because of its air- and moisture-stable, mild reaction conditions, affordable reagents, and non-toxic by-products [1-3]. Therefore, the Suzuki reactions have been gaining much attention. Vasu mentioned that “catalyst is a substance which increases the rate at which a chemical reaction approaches to equilibrium without itself permanently involved” [4]. Research efforts have been continuously aiming at the design and development of catalyst to speed up Suzuki reactions. Accordingly, various novel heterogeneous catalysts have been reported, and the criteria for catalyst evaluation include, but are not limited to, catalytic performance, thermal stability, cost, morphology, and synthetic routes [5-8]. Moreover, the production of biaryl compounds is also affected by the solvent, base and reaction temperature except for catalyst. Therefore, it is important to synthesize efficient catalysts and search optimal reaction conditions towards the synthesis of valuable chemicals. Figure 1 illustrates the applications of Suzuki reactions and the key challenges associated with heterogeneous catalysts in these reactions.

The application of Suzuki reactions as well as key issues of heterogeneous catalyst in Suzuki.
Figure 1. The application of Suzuki reactions as well as key issues of heterogeneous catalyst in Suzuki.

According to reported results, transition metals such as Pd, Fe, Cu, and Ni can effectively catalyze Suzuki reactions with improved catalytic activity and broad substrate scope [9]. These metals are often immobilized or encapsulated within polymer matrices, with typical supports including polymers, graphene oxide, and other carbon-based materials [10-16]. In the heterogeneous catalysis system, the development of support materials undergoes a sequence of changes. Initially, support materials were only considered as stabilizers to anchor or disperse metals. Later, the importance of support materials was realized, and the exploration of support materials is not yet stop because of its complexity [17-21]. The catalytic activity of catalysts is directly or indirectly affected by support materials, which is mainly attributed to electronic interactions between the support materials and the metal.

Recently, support materials functionalized with nitrogen-containing ligands, phosphorus-containing ligands, or hybrid N, P-ligands have attracted considerable interest, and research efforts have been devoted to the preparation of structurally diverse support materials via facile synthetic strategies. It is important to notice that some important factors, such as low cost and availability of precursors, simple synthetic procedures, and non-sensitivity to air, should be considered to meet the commercially viable demands. Apart from these, the geometry (i.e., steric factor) of ligands is also essential, as it has a non-negligible impact on activity. Notably, support materials featuring a high, synthetically tunable surface area can effectively boost catalytic efficiency, owing to the following advantages: (i) furnishing numerous active sites per unit volume to anchor metal species; (ii) maximizing the accessibility of reactant substrates to the catalytic centers. In addition, the nanoscale and shape of transition metals are also critical for the catalytic performance because this is directly linked with high surface area and diverse binding force strength [22]. Typically, Pd is considered as an essential and most powerful tool, and it appears to be among the most popular metals to anchor on support materials so far. In the Suzuki reactions, Pd is often anchored on the support materials in the form of metallic Pd and +2 oxidation state, and familiar Pd precursors include Pd(OAc)2, PdCl2, and so on.

Although heterogeneous catalysts have been widely reported for the Suzuki reactions, there is still a lack of a comprehensive review to summarize recent developments in transition metals supported on functionalized materials for enhancing Suzuki reactions. Here, we will focus on the applications of different kinds of Pd catalysts in Suzuki reactions. The synthesis, characterization, catalytic activity, catalyst reuse, and recyclability of these catalysts will all be discussed in each individual example. In addition, the first-row transition metals-based heterogeneous catalysts (Ni, Cu, Fe, Co) applied in the Suzuki reactions will also be discussed and compared. For easy understanding of the readers, the general mechanism and application of Suzuki reactions in different fields will be shown in the beginning part. This review article aims to provide more insightful information to inspire innovation of catalyst design for Suzuki coupling reactions.

2. History and development of Suzuki reactions

2.1. Fundamentals of Suzuki reactions

Suzuki reactions have gained widespread attention since their discovery in 1979 by Akira Suzuki, especially with application in the industrial synthesis of pharmaceutical drugs, dyes, and agrochemicals. The Suzuki reaction involves the coupling of aryl halides with phenylboronic acids, catalyzed by palladium under appropriate basic conditions. The general mechanism of Suzuki reactions is represented in Scheme 1, and the Suzuki reactions follow a catalytic cycle involving three main steps (oxidative addition, transmetalation, and reductive elimination). Initially, aryl halides react with the active palladium catalyst (oxidative addition) to generate intermediate XLnPdIIAr1 after being adsorbed on the catalyst. Under alkaline conditions, XLnPdIIAr1 reacts with arylboronic acid through transmetalation. Ultimately, the produced intermediate Ar2LnPdIIAr1 undergoes reductive elimination to afford the desired target product, resulting in the initial stage catalyst LnPd0 [23,24].

General mechanism for Suzuki reactions.
Scheme 1. General mechanism for Suzuki reactions.

2.2. Practical applications of Suzuki reactions

2.2.1. Applications in pharmaceutical synthesis

Over the past decade, the Suzuki reactions play a pivotal role in pharmaceutical synthesis. Baricitinib (approved by the U.S. FDA in 2018) is an orally bioavailable drug for the treatment of rheumatoid arthritis and has been demonstrated to reduce mortality in patients with COVID-19 [25]. The Suzuki reaction can be employed in the synthesis of baricitinib, with the synthetic route illustrated in Scheme 2. As shown in Scheme 2, the synthesis of baricitinib involves Suzuki reactions of 2-{1-(ethylsulfonyl)-3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazol-1-yl]azetidin-3-yl} acetonitrile and 4-chloro-7-H-pyrrolo[2,3-d] pyrimidine, using Pd(PPh3)4 catalyst and cesium fluoride (CsF) base in water and toluene under reflux conditions, to give target product with 84%, and the overall yield was as high as 49% [26]. In addition, numerous examples exist in which Suzuki reactions have been employed as a key tool for the synthesis of pharmaceutical intermediates, as shown in Scheme 2, such as treatment of bronchial asthma of roflumilast [27], anticancer drug of tazemetostat [28] and entrectinib [29].

The application of Suzuki reactions for pharmaceuticals.
Scheme 2. The application of Suzuki reactions for pharmaceuticals.

2.2.2. Advances in agrochemical development

Similarly, the Suzuki reaction is also extensively applied in the synthesis of agrochemicals, such as bombykol, boscalid, bixafen, fluxapyroxad, bifenazate [30,31]. For boscalid, the conventional synthetic route comprises three steps, in which the initial coupling of 4-chlorobenzeneboronic acid and 1-chloro-2-nitrobenzene represents a critical step (Scheme 3). Volovych et al. [31] combined single reaction steps to a tandem process in three phase microemulsion system, and the overall yield was up to 90%.

The application of Suzuki reactions for agrochemicals.
Scheme 3. The application of Suzuki reactions for agrochemicals.

2.2.3. Utilization in natural product synthesis

Natural products exhibit significant biological activities, such as male antifertility and inhibition of Human Immunodeficiency Virus (HIV) effects, and the synthesis of these natural products has attracted great attention. Asymmetric Suzuki reactions as a key step are critical to control the axial chirality in the synthesis of many natural products, such as korupensamine A [32], korupensamine B [32], Michellamine B [32], ancistrotectoriline A [33], and (-)-gossypol [34]. Yang et al. achieved facile construction of korupensamine A through Pd-catalyzed asymmetric Suzuki coupling reactions. As shown in Scheme 4, by using 1 mol% Pd (OAc)2 and 1.2 mol % sterically hindered P-chiral monophosphours ligand, asymmetric Suzuki coupling of aryl bromide with arylboronic acid provided the corresponding coupling product in 96% yield and 93% ee. Likewise, korupensamine B was also obtained in a similar manner to korupensamine A. The application of asymmetric Suzuki cross-coupling in the synthesis of ancistrotectoriline A and (-)-gossypol have been also been documented [33,34].

The application of the Suzuki reactions for the synthesis of the natural products.
Scheme 4. The application of the Suzuki reactions for the synthesis of the natural products.

3. Palladium-Based heterogeneous catalysts for suzuki reactions

In a supported metal catalysis system, the choice of support materials is equally important, because support materials can act as not only basis for immobilizing the metals but also as a charge transporter [35]. Fortunately, researchers have recognized that support materials can exert direct or indirect effects on the coupling process, and several studies have explored this at a fundamental level. In addition, the stability of heterogeneous catalysts can be strongly influenced by the interactions between metal species and functional groups on the support material. In this section, the hypercrosslinked polymers (HCPs), polysaccharides, metal organic frameworks (MOFs), and covalent organic frameworks (COFs) materials are mainly discussed in the Suzuki reactions; meanwhile, zeolites and nanotechnology are also briefly discussed. The characteristics of different support materials are summarized in Table 1 [24,35-39].

Table 1. Summary of different support materials.
Materials Characteristics Ref.
Hypercrosslinked polymers Cost-effective, high surface area, time-efficient synthesis, great diversity with tunable property, hierarchical porous structure, and excellent chemical robustness. [35]
Polysaccharides Green nature, low cost, mechanical stability, eco-friendliness, easy availability, high potential for chemical modification, and abundance of reactive free hydroxyl groups. [24]
Ordered porous frameworks

1. COFs: High porosity and specific surface area, high crystallinity, functional diversity, ordered chemical network, tunability of structures, and efficient electron transfer capacity.

2. MOFs: Including metal ions or clusters (nodes), well-defined structures, high porosity and specific surface area, high thermal and chemical stability, and ultrahigh porosity crystals.

 [36,37]
Zeolites Well-defined channels, large specific surface area, adjustable acid-base sites, and high chemical stability. [38]
Fe3O4-based nanotechnology High stability, low cost, facial preparation, high surface-to-volume ratio, low toxicity, and easily functionalized. [39]

3.1. Hypercrosslinked polymers (HCPs) as catalyst supports

The HCPs are permanent microporous polymer materials, and have still undergone increasing attention due to the advantages of structure integrity, diverse synthetic methods, high surface area, and low-cost reagents (monomers and solvents). To date, the major synthetic approaches of HCPs are post-crosslinking polystyrene-based precursors, external crosslinking strategies, and one-step self-polycondensation. The diversity of building blocks and synthetic approaches boosts diverse HCPs, which exhibit great potential in many fields.

3.1.1. Nitrogen-containing ligand-functionalized HCPs

To explore the influence of ligands, Li et al. have executed a thorough study of three Poly-NHC-Pd2+ (N-heterocyclic carbene, NHC) via Suzuki reactions [40]. Firstly, the polymers were prepared by crosslinking three substituted NHCs with benzene, respectively, and the products were then treated with Pd(OAc)2. The successful preparation of support materials was confirmed by 13C cross-polarization magic angle spinning (CP/MAS) NMR and Fourier transform infrared spectroscopy (FT-IR), and Poly-NHC-2-Pd2+ showed high activity within 60 min for iodobenzenes or bromobenzenes with phenylboronic acid. Interesting, catalyst afforded 100% yield for coupling chlorobenzenes and phenylboronic acid in 3 h (Scheme 5). The activity decreased slightly in repeated reactions (five cycles, 99–92%). However, Poly-NHC-1-Pd2+ and Poly-NHC-3-Pd2+ displayed poor performance in the catalyst reuse study (18%–trace, 99–72%, respectively). The electronic effect of the substituents on the NHC and pore distributions plays a key role on the activity and stability of the Pd catalyst. Stronger electron-withdrawing ability of the substituent can stabilize the lone pair of electrons on NHC in a benefic manner, resulting in a more stable coordination bond of NHC-Pd2+.

The Suzuki reactions induced by Poly-NHC-2-Pd2+.
Scheme 5. The Suzuki reactions induced by Poly-NHC-2-Pd2+.

Soon afterwards, the great potential of knitting different N ligands into the HCPs backbone as host material to support Pd was further demonstrated. It was found that Poly-salen-a-Pd(II) displayed excellent catalytic performance for producing biaryl products under aqueous reaction media [41]. In addition, immobilizing Pd onto HCPs that were prepared by knitting 2,2’-bipyridine and benzene was proved to be feasible, and the catalytic performance was significantly enhanced with this HCPs-based catalyst in Suzuki reactions. In addition, owing to the strong coordination between the pyridine motif and PdCl2, the catalyst can be reused at least 5 times without obvious activity loss [42].

1,2,3-Triazoles were selected to form rigid hypercrosslinked polymers using formaldehyde dimethyl acetal as cross-linker, and metalation afforded HCPs-Pd with 1.58 wt% loading of Pd (Figure 2) [43]. The X-ray photoelectron spectroscopy (XPS) analysis of HCPs-Pd manifested that the palladium species was coordinated in the amorphous matrix of HCPs in the +2 oxidation state. An excellent catalytic performance was observed in Suzuki reactions of iodo- and bromobenzenes (91–99%, ethanol (EtOH)/H2O, 60°C, 1 h), and a turnover number (TON) value up to 1.66 ×104 was obtained. The reusability test demonstrated the stability of this catalyst. It was found in this example that a porous structure might positively influence the activity of catalysts in Suzuki reactions. The large number of micropores leads to more efficient dispersion of palladium nanoparticles, resulting in better catalytic efficiency.

The application of HCPs-Pd catalyst.
Figure 2. The application of HCPs-Pd catalyst.

Fu et al. prepared sulfonate-functionalized HCPs by the Friedel–Crafts reaction using N, N-(benzyl) (propanesulfonate)imidazolium as the monomer and methyl as crosslinker, and sulfonate-functionalized HCPs were then used to encapsulate Pd (Figure 3) [44]. The as-prepared Poly-BBIS-Pd2+ was characterized with XPS, which confirmed the presence of Pd(II) (binding energies: 338.6 and 343.8 eV) and Pd(0) (binding energies: 336.6 and 342.5 eV). Benefiting from the high surface area (542 m2/g), a satisfactory catalytic performance was found in Suzuki reactions, and a TON value of 4291 was still achieved after reusing five times. However, the catalyst displayed substrate selectivity; negligible product was observed for the reaction of bromobenzene and 2,6-dimethylphenylboronic acid. Furthermore, recyclability (100–94%, five cycles) and the hot filtration test demonstrated the heterogeneous nature of this catalysis system. The outstanding catalytic performance and stability can be attributed to the electron-rich environment for palladium provided by sulfonate-functionalized HCPs.

Schematic illustration of the synthesis of Poly-BBIS-Pd2+.
Figure 3. Schematic illustration of the synthesis of Poly-BBIS-Pd2+.

Liu et al. fabricated a series of nitrogen-functionalized HCPs through Friedel–Crafts reaction using formaldehyde dimethyl acetal (FDA) as crosslinking reagent (Figure 4) [45]. The SBET of the HCPs before and after loading Pd are in the range of 600–774 m2/g. Due to the formation of a six-membered ring by Pd2+ and the bidentate ligands of NHC and pyridine, high surface area, and porous structure, superior catalytic performance was found in the Suzuki reactions (85–98%, H2O, 80°C, 1 h). In addition, HCP-Pd-I displayed higher recyclability than congener catalysts (HCP-Pd-II and HCP-Pd-III); this catalytic system can be recycled at least five times with a yield of > 93%. These results indicate that the stability is associated with the electronic effects of substituents on the NHC and the cross-linking density. NHC ligands bearing stronger electron-withdrawing substituents enhanced the stabilization of the coordination bond between NHC and Pd2+. Furthermore, benzyl and phenyl moieties on the NHC can provide additional cross-linking sites, resulting in more stabilization. More importantly, three catalysts showed different efficiency for the coupling of iodobenzene with phenyl boronic acid (HCP-Pd-I: 95%; HCP-Pd-II: 90%; HCP-Pd-III: 88%), indicating that the activity of catalyst could be affected by pore size.

Schematic illustration of the synthesis of three HCP-Pd catalysts.
Figure 4. Schematic illustration of the synthesis of three HCP-Pd catalysts.

A triazatruxene-based framework (triazatruxene hypercrosslinked polymer, TATHCP) was built through Friedel–Crafts alkylation and then utilized to coordinate Pd (Figure 5) [46]. The resulting TATHCP-Pd had an ordered 2D stacking sequence and exhibited desirable catalytic activity. In a limited study regarding on Suzuki reactions of aryl bromide with phenylboronic acid, high yields were obtained in the range from 90% to 98%. In addition, TATHCP-Pd was reused up to 4 runs (98–94%, avg. yield 96%, 4 cycles), which was attributed to the coordinating effect of the nitrogen functionalities of planar triazatruxene and steric limitation for Pd(OAc)2 from the pores of the polymer network.

Schematic illustration of synthesis and application of hypercrosslinked ordered organic catalysts.
Figure 5. Schematic illustration of synthesis and application of hypercrosslinked ordered organic catalysts.

3.1.2. Phosphorus-containing ligand-functionalized HCPs

By using triptycene and triphenylphosphine as reagents, Mondal et al. synthesized an aryl network polymer (KAP) as Pd support material by an external crosslinking strategy (Figure 6) [47]. The SBET of the KAP was found to be 965.077 m2/g. After introducing Pd, the SBET was decreased to 493.477 m2/g. XPS analysis confirmed that the Pd ions are coordinated with phosphorus atoms. In Suzuki reactions, this catalyst afforded high yields up to 96% of aryl halide in green solvent (EtOH: H2O 1:1) at room temperature. Importantly, this catalyst also showed excellent catalytic performance for the synthesis of precursors of Valsartan and Boscalid (> 86%). The excellent performance in Suzuki coupling of aryl halide with arylboronic acid demonstrates the beneficial effects of the abundant microporous structure and phosphorus-containing functional groups. In most cases, Pd species are introduced after the formation of HCPs, which enables Pd to be anchored at the most accessible sites [48]. Wang et al. found that it is possible to incorporate metal complex (Pd(PPh3)4) into HCPs skeleton with FDA as crosslinking reagent in the presence of FeCl3, and this strategy ensures the original structure of the Pd(PPh3)4 to a large extent [49]. This catalyst is potential in terms of catalytic performance and durability (recycled at least 8 times).

Schematic illustration of the synthesis of KAP and the corresponding Pd loaded catalyst.
Figure 6. Schematic illustration of the synthesis of KAP and the corresponding Pd loaded catalyst.

Li et al. also prepared a series of functional microporous organic polymers through Scholl reaction of sym-PhPh3 with AlCl3 as a catalyst [50]. As shown in Figure 7, in the Suzuki couplings of chlorobenzene derivatives with arylboronic acid, catalyzed by the P-functionalized catalyst, high yields of 91–99% were obtained by using 0.1 mol% Pd (K3PO4⸱3H2O, EtOH/H2O, 80°C, 2–4 h). In addition, the use of EtOH/H2O supports the perspective of green chemistry. The catalyst stability was evaluated in four consecutive recycling runs, and no obvious loss of activity was observed. Moreover, Pd leaching experiment further confirmed that the Suzuki reaction was catalyzed by the heterogeneous catalyst rather than free PdCl2.

Suzuki reactions performed by using Pd loading HCPs from triphenylphosphine.
Figure 7. Suzuki reactions performed by using Pd loading HCPs from triphenylphosphine.

In a study reported by the Xu group [51], a triphenylphosphine ligand was knitted into the polymer via an external cross-linking reaction. Subsequently, metallization of this solid material was performed by using PdCl2. Structural characterization, FT-IR, X-ray diffraction (XRD), as well as XPS measurements (342.9 eV, assigned to Pd 3d3/2), verified the successful preparation of the catalyst and Pd introduction. As demonstrated by the results of Brunauer-Emmett-Teller (BET), triphenylphosphine-based microporous organic nanotube frameworks supported Pd catalysts MONF-PPh3@Pd (triphenylphosphine-based microporous organic nanotube frameworks supported Pd catalysts) and MONF-PPh3@Pd-2) contain micro- and mesopores with a total pore volume of 0.70 cm3/g and 1.07 cm3/g, respectively. The sufficient space inside the framework increased the accessibility of the reactant to active sites. The obtained catalyst was tested in Suzuki reactions, and yields of 87–99% and turnover frequency (TOF) of 121-1650 h-1 (0.12 mol% Pd, EtOH/H2O 3:2, K2CO3, 80°C, N2 protection) were obtained (Figure 8), indicating superior activity of MONF-PPh3@Pd-1 for coupling aryl halides with phenylboronic acid. The morphology of MONF-PPh3@Pd-1 recovered after five runs was well maintained, and negligible Pd leaching (0.0009 mg/L) was found in a hot filtration experiment after the first cycle, and very low Pd leaching offered significant advantages for large-scale industrial applications. The good recyclability of MONF-PPh3@Pd-1 is related to its microporous nanotube structure with tunable size and tight lock of Pd by triphenylphosphine function.

Suzuki reactions were performed by using triphenylphosphine-based microporous organic nanotube frameworks supported by Pd catalysts.
Figure 8. Suzuki reactions were performed by using triphenylphosphine-based microporous organic nanotube frameworks supported by Pd catalysts.

3.2. Polysaccharide-based catalytic systems

Polysaccharides have long been widely used as catalyst supports or precursors in heterogeneous catalysis systems. An important reason for extensive application is their biodegradability, abundant materials in earth, and biocompatibility. The study of polysaccharides, such as cellulose [52], alginate [53], starch [54], pectin [55], chitosan [56], and chitin [57], increases steadily, because hydroxyls group of polysaccharides could be utilized for bonding with numerous functional groups. In this section, the modification of polysaccharides and application for constructing aryl-aryl linkages are highlighted, and the functional groups involved in the modification of polysaccharides are listed in Scheme 6.

The functional group units are grafted onto the functionalized polysaccharides.
Scheme 6. The functional group units are grafted onto the functionalized polysaccharides.

Trimethylammonium chloride pendant groups were immobilized on cellulose fibers, and acted as active sites for grafting PdCl2 to prevent Pd leaching [58]. The obtained polymeric catalyst (Pd@C-CNF) displayed an outstanding performance for constructing aryl-aryl linkages using K2CO3 for 4 h (0.1 mol% Pd, 68–98%), but high temperature (110°C) is needed in order to get a good yield. Acquired by XPS and transmission electron microscopy (TEM), cellulose nanofibrils effectively limited the aggregation of Pd nanoparticles (Figure 9). Considering the fact that the NHCs have a greater tendency to coordinate transition metals due to their strong nucleophilic nature, an N-heterocyclic carbene functionalized cellulose was designed to support palladium [59]. The obtained catalyst (HEC-NHC-Pd) showed excellent C-C coupling capacity in EtOH/H2O solvent (TON: 50–247; TOF: 12–247 h-1). However, a decrease in its catalytic activity was observed in the recycle experiments of the catalyst. The slight aggregation of Pd was also observed after four cycles. Fortunately, very low Pd leaching validated that Pd was strongly grafted by dual coordination sites (-OH and N-methylimidazole) (fresh catalyst :7.19 wt% Pd, fourth cycle: 7.14 wt% Pd).

Suzuki reactions performed by Pd@C-CNF.
Figure 9. Suzuki reactions performed by Pd@C-CNF.

The surface-modification of cellulose/Al2O3 was reported by Mhaldar [60]. The host material (chloropropyl-Cell@Al2O3) was synthesized by the reaction of 3-chloropropyl-triethoxysilane with cellulose/Al2O3. Then, surface functionalization of the host material was performed by grafting 2-aminopyridine, which provided a strong binding ability to coordinate Pd. Therefore, the as-prepared Pd(II)-AMP-Cell@Al2O3 could be reused for 5 cycles in Suzuki reactions with minor loss of Pd (< 3%), but the reaction was carried out in the solvent of dimethyl formamide (DMF).

The primary advantage of cellulose as a support lies in its abundant hydroxyl groups, which facilitate the formation of silane-modified cellulose (Cell-NH2) via reaction with 3-aminopropyltriethoxysilane (APTES). This is followed by a Schiff base reaction to generate C=N. According to this method, in 2016, Baran et al. reported the synthesis and characterization of Schiff-functionalized cellulose catalyst (CL-Sc-Pd), and the catalyst exhibited high catalytic performance towards various C-C reactions assisted by microwave technique [61]. Later, Dong et al. introduced organic units of 4-(2-Pyridinyl) benzaldehyde onto Cell-NH2 to construct silane-modified cellulose Schiff base biomaterials. By using Na2PdCl4, Cell-Sb-Pd(II) was prepared easily [62]. The catalytic activity of the Cell-Sb-Pd(II) catalyst was tested in the Suzuki reactions, and TOF varied between 53 h-1 and 682 h-1 (Figure 10). For chlorobenzene, the catalyst showed inferior catalytic activity. A mercury poisoning study was performed in the reaction of p-bromoanisole with phenyl boronic acid, and a significant change of yield was not observed after adding mercury, indicating the heterogeneous nature of Cell-Sb-Pd(II). Owing to the strong interaction of Pd and multiple capturing sites (-OH, Schiff base, and pyridyl moieties), Pd leaching (< 1%) was effectively prevented in the recycle experiments (fresh catalyst: 1.93 wt% Pd, fifth cycle: 1.92 wt% Pd). Another study about exploring Cell-Sc-Pd(II) activity in Suzuki reactions was also reported [63]. Similar to reports as discussed above [61,62], support material was obtained by Schiff base reaction of 2-hydroxy naphthaldehyde and Cell-NH2. In terms of yield and recyclability, the final catalyst of Cell-Sc-Pd(II) possesses great potential (97–74%, 5 cycles). Such a method for constructing Pd heterogeneous catalysts with readily available and green cellulose as support possesses great potential for industrial application.

1.93% Cell-Sb-Pd(II) inducing Suzuki reactions.
Figure 10. 1.93% Cell-Sb-Pd(II) inducing Suzuki reactions.

Baran et al. reported the preparation and application of a related Schiff base chitosan catalyst [64]. Based on the report [65], the synthesis of chitosan matrix involved the following three steps: ⅰ) preparation of ligands with a carbonyl group, ⅱ) grafting ligands onto deacetylated chitosan, ⅲ) immobilizing Pd. The obtained OCMCS-3aPd displayed promising catalytic activity in Suzuki reactions. The coupling of iodo- or bromobenzenes provided medium to high yields of 37–97% (TON: 1275–2450). However, the yields decreased from 97% to 73% in a 10-runs reuse study. The application of palladium coordinated with starch materials as catalysts for Suzuki reactions has also attracted great interest. Baran [66] treated starch with APTES and then introduced 2,4-dihydroxybenzaldehyde, behaving as Schiff bases. After introducing of Na2PdCl4, the final catalyst afforded satisfactory performance in Suzuki reactions at 50°C, and even the reactions of chlorobenzenes gave product yields of 43–90%. In a reuse study, a gradual decrease of activities was found in ten runs (100–62%, avg. yield 82%), which can be ascribed to Pd leaching.

3.3. Ordered porous framework-supported catalysts

Ordered porous frameworks have been emerging as potential materials to mono-disperse Pd metal, such as COFs and MOFs. COFs are a class of well-designed materials with long-range ordered molecular structures [67], and MOFs are porous crystalline materials with uniform pore sizes, large surface area, and functional organic linkers [68].

3.3.1. Covalent organic frameworks (COFs)

COFs not only is tolerant and robust, but also versatile to coordinate many metal ions. A new phosphine covalent organic framework (P-COF) was synthesized with imine-bonds as linkers. Owing to electron-rich heteroatoms (P, N), Pd was securely anchored within the walls of P-COF [69]. Characterization, such as 13C CP/MAS NMR, power X-ray diffraction (PXRD), nitrogen adsorption-desorption, and XPS measurements (337.8 eV), confirmed satisfactory structural features of P-COF and resulting Pd(OAc)2/P-COF. The Pd(OAc)2/P-COF afforded excellent yields (84–100%) for constructing C˗C bonds at room temperature for 3 h. Owing to its porous nature and heteroatoms (P, N) coordination sites, the yield of bromobenzene and phenylboronic acid could still achieve above 93% at the fifth cycle. Additionally, according to result of 13C CP/MAS NMR, the chemical structure was almost maintained after five cycles.

The Li group [70] reported the synthesis of a yolk-shell structure catalyst. Briefly, Pd nanoparticles were deposited on uniform carbon microspheres, followed by treating this matrix with silica ((Pd/C)@SiO2), and COFs were then coated on the (Pd/C)@SiO2 as a shell. Finally, silica interlayers were removed by HF etching, which afforded a (Pd/C)@TpPa COFs catalyst with molecular-size selectivity due to the pore structure of protective layer COFs (Figure 11). Satisfactory characterization results were collected from PXRD, BET, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) mapping, TEM, and thermal gravimetric analysis (TGA) measurements. In catalytic tests, (Pd/C)@TpPa COFs exhibited brilliant substrate size selectivity and excellent productivity in Suzuki reactions (Table 2) [70-72]. The yields did not decrease sharply over five cycles, owing to the protection of TpPa COFs: the confined space facilitated the recapture of leached Pd atoms. Furthermore, the porous structure of the TpPa COF shell enabled substrate screening and modulated mass transfer.

Schematic illustration of the synthesis of (Pd/C)@COFs and application in Suzuki reactions.
Figure 11. Schematic illustration of the synthesis of (Pd/C)@COFs and application in Suzuki reactions.
Table 2. Application of COFs-based catalysts in Suzuki reactions.
Entry Catalyst Yields (%) a Runs Pd (mol%) Conditions Ref.
1 (Pd/C)@TpPa COFs 87 5 0.05 EtOH/H2O (2:1), 80°C [70]
2 Pd/COF-SMC2 96 3 0.5 Ethanol, 80°C [71]
3 Pd@COF-QA 99 10 1.7 H2O, 50°C [72]

a: Phenylboronic acid and bromobenzene

The solvothermal method was utilized to fabricate a series of palladium-COFs samples with well-designed structures [71]. Characterization, including FT-IR, PXRD, and XPS measurements (N 1s and O 1s), confirmed satisfactory structural features of COF-SMC2 that was synthesized from 1,3,5-triformylphloroglucinol and p-phenylenediamine. Pd/COF-SMC2 displayed high catalytic activity in Suzuki reactions. This catalyst enabled the synthesis of over 20 halo-substituted biaryl products in moderate to excellent yields in ethanol at 80°C (Table 2) [70-72].

Wang et al. successfully designed a Pd loaded and paraffin-chain quaternary ammonium salt decorated covalent framework (Pd@COF-QA) and applied it in the Suzuki reactions [72]. In the initial stage, COF-QA was synthesized through the Schiff-base condensation between quaternary ammonium salt decorated dihydrazide and 1,3,5-triformylbenzene. After finishing the Schiff-base condensation step, Pd(OAc)2 was incorporated into porous COF. The synthesized Pd@COF-QA was tested in the Suzuki reactions, and afforded high yields for coupling substituted iodo- and bromobenzenes with phenylboronic acid (1.7 mol% Pd, triethylamine (TEA), H2O, 50°C, 6 h, in air), but only medium yields of 42–63% were observed in the reaction of -NO2, -OMe, -CHO and -CN substituted chlorobenzenes. In the reuse study, there is ca. 5% Pd loss after the 10th run, and structural characterization data of the catalyst recovered after reuse, acquired by PXRD, high resolution transmission electron microscopy (HR-TEM), and SEM, confirmed stability of the Pd@COF-QA structure.

3.3.2. Metal–organic frameworks (MOFs)

MOFs featuring favorable mass diffusion properties and ultrahigh specific surface areas have emerged as promising materials in both academic research and industrial applications, and have been widely employed in heterogeneous catalysis, drug delivery, and chemical sensors [73,74]. The structure of MOFs can be tuned by varying their building units, which opens an avenue for researchers to design and utilize various MOFs as catalyst supports in Suzuki reactions.

As reported by Chen and coworkers [75], a MOF-253 sample was synthesized via hydrothermal reaction of AlCl3·6H2O and 2,2-bipyridine-5,5-dicarboxylic acid. The resulting material showed a high surface area of 1152 m2/g, and the surface area decreased to 912 m2/g upon loading PdCl2, which indicated that the Pd was successfully encapsulated by MOF-253 supports, and the presence of Pd was further confirmed by XPS analysis. The MOF-253·0.05PdCl2 catalyst showed excellent activity in Suzuki reactions, but a long reaction time (20 h or 30 h) was needed for the transformation of aryl chlorides (85–96% yields). The catalytic efficiency of MOF-253·0.05PdCl2 is higher than that of Pd(bpy)Cl2 and PdCl2(CH3CN)2, as related to electron transfer between adjacent ligand and Pd in the MOF catalyst. In successive run tests, a significant decrease in catalytic activities was not observed. Moreover, no further reactivity was found in a hot filtration test, and a very low amount of Pd (< 0.1%) was measured in the reaction solution with atomic absorption spectroscopy (AAS).

The functionalized MOF-808 materials have drawn extensive attention [76]. Wang and coworkers fabricated a MOF-808 sample by heating 1,3,5-benzenetricarboxylic acid (H3BTC) and ZrOCl2·8H2O in H2O/acetic acid. A Pd-functionalized Pd@MOF-808 was accordingly prepared for catalyzing Suzuki reactions [76]. According to the PXRD pattern, the crystal structure of MOF-808 was well preserved after Pd loading. Importantly, TEM images gave evidence that Pd had a uniform size of about 7 nm on the octahedral crystal MOF-808. The catalytic performance of Pd@MOF-808 was tested in Suzuki reactions of aryl halides with arylboronic acids in methanol, which afforded low to excellent yields except for aryl chlorides (29–99%). The reaction of p-iodoanisole and phenylboronic acid was selected as a model reaction to check the stability of the catalyst. This catalyst gave good performance in the first five runs, and the yields decreased to 49% at sixth run, which is speculated that the surface of Pd nanoparticles (Pd NPs) was covered by halide ions.

UiO-66, Zr-based MOF, is a rich family of porous materials composed of Zr-based building units and functionalized terephthalic acids, which is a highly promising material to encapsulate Pd NPs for Suzuki reactions [77-79]. Two chiral proline-decorated bifunctional Pd@NH2-UiO-66 catalysts, synthesized by the encapsulating Pd and introduction of chiral proline, showed excellent activity for sequential Suzuki/asymmetric aldol reactions (Figure 12) [79]. Pd@NH2-UiO-66(pro)-1 was prepared via a one-pot “bottle-around-ship” solvothermal method, in which chiral proline was coordinated to Zr nodes. In contrast, Pd@NH2-UiO-66(pro)-2 was synthesized via the amidation reaction between N-Boc-L/D-proline and Pd@NH2-UiO-66, followed by the removal of Boc groups. PXRD, FT-IR, TEM, N2 adsorption-desorption isotherms, and XPS results confirmed the successful synthesis of materials. At a low Pd@NH2-UiO-66(pro)-1 amount (2 mg, 1.46 wt% Pd), excellent performance was observed in sequential Suzuki coupling/asymmetric aldol reactions (yield: 94–99.9%, eeanti: 57–97%). In addition, the structure collapsed of the recovered catalyst was not detected in the PXRD patterns, and no decrease in activity was observed in four cycles.

Structure of chiral proline-decorated bifunctional Pd@NH2-UiO-66 and application in sequential Suzuki/asymmetric aldol reactions.
Figure 12. Structure of chiral proline-decorated bifunctional Pd@NH2-UiO-66 and application in sequential Suzuki/asymmetric aldol reactions.

3.4. Other functional material-based catalysts

In this section, a few other materials were illustrated in the form of individual examples. Zeolites are crystalline aluminosilicates with cavities and cages [80]. They have been attracted wide attention in catalysis due to the property of encapsulating metal nanoparticles. The major types of zeolites include Y-zeolite, Beta, ZSM-5, ZSM-35, and mordenite. However, the transfer of substrate to the active center in zeolites was sometimes limited due to the small size of the pores. Wang and co-workers reported the fabrication of Pd@USY through traditional ion-exchange between USY zeolite (Molecular sieve, Si/Al mol ratio: 3.2) and Pd(NH3)4Cl2∙H2O, followed by activating in situ [81]. After the above treatment, Pd was migrated to the surfaces, which was confirmed by TEM and XPS analysis. Owing to the migration of Pd from inside to the surface of the zeolite, the diffusion path of reactants was short; thus, the activated Pd@USY showed good catalytic performance in the Suzuki reaction (95–99%), and the aggregation of Pd was suppressed.

Nanotechnology is a unique combination of material science and engineering, and is being considered to enrich its wide application by designing green and safe nano products [82,83]. In this context, a series of palladium@Fe3O4 type catalysts was prepared by complex encapsulating Fe3O4 spheres and applied in the Suzuki reactions [83].

4. First-Row transition metal catalysts for suzuki reactions

As builders of C-C coupling reactions, the potential and importance of Pd-based catalysts is nonnegligible. The drawbacks here are the lability, precious, lack of resources, and harmfulness. In this section, the cheaper Ni, Co, Cu, and Fe heterogeneous catalysts are discussed and compared. Certainly, as sustainable alternatives to Pd, the modified bimetals for catalyzing Suzuki reactions are also extremely appealing. The corresponding low-cost first row transition metals-based catalysts are summarized in Table 3 [84-95].

Table 3. Comparison of related catalysts in the Suzuki reactions.
Entry Catalyst Conditions Yield (%) TOF (h-1) Cyclesa (times) Ref.
1 Pd-Fe/BNNS (CH3)3COK, EtOH/H2O, reflux, 0.5 h 99 9900 6 [84]
2 Cu (Fe-Cl)/Al K2CO3, EtOH, 78°C, 32 h 58 - 8 [85]
3 PCLZC-3 K2CO3, EtOH: H2O=4:3, 80°C, 1 h 8.44 201.59 10 [86]
4 Pd-Cu NWs K2CO3, DMF: H2O=1:1, 80°C, 2 h 99 - 5 [87]
5 Fe3O4@C@Arginine-Cu0 KOH/Ba(OH)2/Ca(OH)2/Mg (OH)2, H2O, room temperature, 2 h 98 - 6 [88]
6 Cu-CA-MOF KOH, DMSO, 120°C, 220 min 86 - - [89]
7 [CuBpm·2H2O]n K2CO3, DMSO, 70°C, 20 min 93 1396 4 [90]
8 Cu-TAPB-BTDA-COF K2CO3, EtOH, room temperature, 2.5 h 54 - 10 [91]
9 Ni (II)-a-diimine-POP K3PO4·3H2O, toluene, 100°C, 12 h 94 - 5 [92]
10 UiO-66 (L3), Ni(COD)2, PPh3 K2CO3, CH3CN, 65°C, 12 h 93 - 7 [93]
11 UiO-66 (L3), NiCl2, PPh3 K2CO3, CH3CN, 65°C, 12 h 90 - 7 [93]
12 GOF@Dm2@PdNi K2CO3, EtOH: H2O=1:2, room temperature, 15 min 97 - 5 [94]
13 Co-His@MNPs/Ch K3PO4, PEG, 80°C, 2h 94 19.6 - [95]

a: Cycles refer to Suzuki reactions (not specifically bromobenzene and phenylboric acid) catalyzed by catalysts.

In 2017, Fu et al. [84] demonstrated that anchoring Pd-Fe core-shell bimetallic nanoparticles on boron nitride nanosheets (BNNS) is a promising strategy for the synthesis of biaryl derivatives. A series of reactants was tested in the Suzuki reactions, and yields of 84 –100% were obtained. The high efficiency of the catalyst is attributed to synergistic effects and electronic interactions. Moreover, the synthesized Pd-Fe/BNNS possessed good stability (six cycles, avg. yield > 90%), and low metal losses (Pd < 10%, Fe approximately 5%) were measured.

In the same year, Lamei et al. [88] explored the activity of arginine-modified Fe3O4@carbon supported copper/ppm palladium in the Suzuki reactions. Owing to the introduction of arginine amino acid, 0.1 mol% Fe3O4@C@arginine-Cu0 afforded high yields for coupling iodinated or brominated substrates with phenylboronic acids (> 92%). In addition, the catalyst could be recovered at least six runs (99–93%, avg. yield 95.7%) by magnetic separation.

Liu et al. [90] prepared a Cu complex based on 2,2’-bipyrimidine ([CuBpm·2H2O]n) heterogeneous catalyst and extended the studies of catalytic efficiency and recyclability through Suzuki reactions. The FT-IR, SEM, and XRD studies confirmed the successful fabrication of the catalyst. The above catalyst afforded desirable yields of 75–98% and TOF values of 709–1441 h-1 by using 0.2 mol% catalyst (K2CO3, dimethylsulfoxide (DMSO), 70°C, 19–37 min). In a 4-run reuse study for the coupling of bromobenzene with phenylboronic acid, the catalytic activity decreased slightly from 93% to 87% (avg. yield 89.5%).

As reported by Feng, the TAPB-BTDA-COF was synthesized by reacting BTDA (4,4’-(benzothiadiazole-4,7-diyl) dibenzaldehyde) with TAPB (1,3,5-tris-(4-aminophenyl)-benzene) [91]. A supported Cu catalyst, Cu-TAPB-BTDA-COF, was then prepared with using this COF material as the support. The resulting catalyst was thoroughly characterized by appropriate instrumental techniques, such as SEM, EDS mapping, XPS, FT-IR, and nitrogen adsorption–desorption experiment. It was found that the channel of supports was not blocked by Cu species. The 93% yield was obtained in the presence of this Cu-based catalyst at room temperature. Furthermore, a heterogeneous system was demonstrated with 0.05% Cu lost after reaction.

Hajipour et al. [95] prepared several magnetically recoverable cobalt catalysts using magnetic-biopolymer as support, which was applied in Suzuki reactions. It was found that Co-His@MNPs/Ch is more efficient, and exhibited good catalytic performance in a range of aryl halides with arylboronic acids using K3PO4 at 80°C for 2 h. Furthermore, a density functional theory (DFT) study confirmed that the Co-His@MNPs/Ch catalyst was better than other Co-ligand@MNPs/Ch catalysts, which is consistent with the experimental results.

5. Conclusions

In summary, Suzuki reactions play a critical role in practical production. Accordingly, many novel support materials anchored metal species have been designed and tested in the Suzuki reactions. In this review, the potential of Suzuki reactions is comprehensively demonstrated, and key insights into various heterogeneous catalysts employed in Suzuki reactions are systematically summarized. Indeed, heterogeneous catalysis is expected to hold considerable promise for Suzuki reactions, and ample opportunities remain for the design of novel and practical heterogeneous catalysts.

So far, numerous excellent catalysts have been reported and utilized mostly in laboratories for coupling small molecular, less frequently in the scale up to real coupling. Hence, testing the catalytic activity of Pd-based catalysts in a practical synthesis route will be more meaningful. In addition, investigating the interactions between support materials and metal species in these catalysts is equally critical, as it enables a more rational design of support materials. The quest for explaining the relationship between support materials and performance is ongoing, with a need for more comprehensive studies into the interaction between support materials and metals.

Finally, considering the practical application of these catalysts, the major issues are reuse and cost. As highlighted in this review, the catalysts exhibited varying cycling stabilities. Further related studies are recommended to perform more detailed characterizations of the catalysts before and after application, thereby deepening the mechanistic understanding. In addition, the development of efficient, cheaper first-row transition-metal-based catalysts should attract much attention, and the availability of catalyst precursors should be considered.

Acknowledgement

This research was supported by the Talent fund of Anhui Polytechnic University (2020YQQ058, 2021YQQ050), the University students’ innovation and entrepreneurship training program (202410363062, S202410363257), Natural Science Foundation of Anhui Province (2108085QB54), and Foundation of Anhui Province Key Laboratory of Clean Catalytic Engineering (LCCE-05).

CRediT authorship contribution statement

Zhanao Lv: Conceptualization, funding acquisition, resources, data curation, writing - original draft. Yahao Dong: Resources, supervision. Tao Li: Data curation, investigation, writing-review & editing. Jiajun Bi: Conceptualization, funding acquisition, supervision, resources, writing - review & editing.

Declaration of competing interest

There are no conflicts of interest.

Data availability

Data will be made available on request.

Declaration of generative AI and AI-assisted technologies in the writing process

The authors confirm that there was no use of artificial intelligence (AI)-assisted technology for assisting in the writing or editing of the manuscript, and no images were manipulated using AI.

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