Pyridinyl functionalized MCM-48 supported highly active heterogeneous palladium catalyst for cross-coupling reactions

Abstract

An MCM-48 supported 2-pyridinylmethanimine Pd-catalyst was found to be a highly efficient catalyst in the Mizoroki–Heck, Suzuki–Miyaura and copper-free Sonogashira cross-coupling reactions of aryl halides under aqueous reaction conditions. The catalyst efficiently promoted these coupling reactions with ppm levels of palladium to afford the corresponding coupling products in up to 98% yield. The supported Pd-catalyst was readily recovered and reused several times without significant loss of its catalytic activity.

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1. Introduction

Palladium is the most popular metal catalyst widely used in numerous organic syntheses due to their applications in organic synthesis,^1–3 material science,⁴ photochemistry,⁵ and in the pharmaceutical industry.^6–10 Among them, the Mizoroki–Heck,^11–15 Suzuki–Miyaura,^16–20 and Sonogashira^21–25 coupling reactions play important roles in modern synthetic chemistry. These cross-coupling reactions generally proceed in the presence of a homogeneous palladium catalyst. One practical limit to perform homogeneous catalysis reactions is the difficulty of separation the product from catalyst and reuse of the catalyst. From the standpoint of environmentally benign organic synthesis, the development of highly active and easily reusable immobilized catalysts, as well as solvent-free reactions are significant interest to chemists. To overcome these problems, chemists have investigated the employment of various heterogeneous palladium species.^26,27 The development of heterogeneous metals supported on materials, such as carbon²⁸ nanotubes,^29,30 graphene,^31–33 silicates,^34–37 polymers,^38,39 metal oxides^40,41 and various hybrid nanocrystals composed of different materials, have been reported.^42–45 Alternatively, metal complexes bound to a ligand anchored on a support have also been studied as a recyclable catalyst.^46,47 Palladacycles have recently emerged as one of the most promising classes of catalysts or catalyst precursors in the Pd-catalyzed C–C bond formation reactions such as the Mizoroki–Heck,^48–51 Suzuki–Miyaura,^52–55 and Sonogashira reactions.^56–58 Nevertheless, only a few examples of Suzuki–Miyaura, Mizoroki–Heck, and Sonogashira reactions, by using water as the solvent, have been reported in previous studies.^59,60 A common strategy to prepare a heterogeneous catalyst consists of anchoring the conveniently modified transition metal complexes onto an insoluble support with the provided anchoring procedure, which maintains the intrinsic activity and selectivity of the catalytic center.^61,62

Recently, mesoporous MCM materials with uniform nanosized pore diameters and high specific surface areas have become of high interest as inorganic supports.^63–65 MCM-41 silica has recently been used as a solid support for the immobilization of the catalysts.^66,67 On the other hand, cubic-structured mesoporous MCM-48 silica has received less attention due to difficulties in the synthesis.^68–70 Owing to its unique three-dimensional pore structure, MCM-48 may be more advantageous than MCM-41. MCM-48 with three-dimensional nanosized pore networks and high specific surface areas would be highly interesting in this area. Herein, we report MCM-48 supported Pd-catalyzed Mizoroki–Heck, Suzuki–Miyaura and Sonogashira cross-coupling reactions, where the quantitative products were achieved with 130 to 400 mol ppm of the catalyst under aqueous reaction conditions. The easy preparation of the catalyst, its long shelf-life, its stability in air, and its compatibility with a wide variety of aryl halides make it ideal for the abovementioned reactions.

2. Experimental

2.1. General information

All manipulations were performed under atmospheric conditions unless otherwise noted. Reagents and solvents were obtained from commercial suppliers and used without further purification. Water was deionized using a Millipore system to Milli-Q grade. PdCl₂ was purchased from Aldrich chemical industries, Ltd. Proton nuclear magnetic resonance (¹H NMR, 500/400 MHz) and carbon nuclear magnetic resonance (¹³C NMR, 125 MHz) spectra were measured using a JEOL JNM ECA-500/400 spectrometer. The ¹H NMR chemical shifts were reported relative to tetramethylsilane (TMS, 0.00 ppm). The ¹³C NMR chemical shifts were reported relative to deuterated chloroform (CDCl₃ 77.0 ppm). Elemental analyses were performed on a Yanaco CHN Corder MT-6 elemental analyzer by the chemical analysis team in Rikagaku Kenkyūjo (RIKEN), Wako, Japan. Inductively coupled plasma atomic emission spectrometry (ICP-AES) was performed on a Shimadzu ICPS-8100 equipment by the chemical analysis team in RIKEN Wako, Japan. N₂ adsorption–desorption isotherms were measured using a BEL SORP mini II analyzer at liquid N₂ temperature. Surface area (S_BET) was calculated by the BET method, the pore volume (V_p) was determined by nitrogen adsorption at a relative pressure of 0.98, and the average pore size (D) was determined from the desorption isotherms using the Barrett–Joyner–Halenda (BJH) method. XPS spectra were measured using an ESCALA 250 (Thermo Fisher Scientific K.K.) by the cooperative support team in RIKEN. The energy dispersive spectroscopy (EDX) was examined using the JEM-2100F, Inha University, Korea. The gas chromatography-mass spectrometry (GC-MS) was measured using an Agilent 7860A/JEOL JMS-T100GC equipped with a capillary column (DB-Wax, 0.25 mm i.d. × 30 m or HP-1, 0.32 mm i.d. × 30 m). Thin layer chromatography (TLC) analysis was performed on a Merck silica gel 60 F₂₅₄. Column chromatography was carried out on a silica gel (Wakogel C-300).

2.2. Preparation of the MCM-48 silica

MCM-48 silica was prepared according to the previously reported method.⁷¹ The resultant silicate mixture was stirred for 1 h at room temperature and the samples were then collected by filtration and transferred to a Teflon lined steel vessel. The sample was then heated at 100 °C for 4 days. The mixture was cooled at room temperature and the precipitated products were washed with DI water and calcinated at 500 °C for 8 h. The MCM-48 was characterized by XRD and TEM.

2.3. Preparation of the 3-aminopropylated MCM-48 silica 1

Fresh calcinated MCM-48 silica (1.0 g) was added to a solution of 3-(aminopropyl)triethoxysilane (0.65 mmol) in toluene (20 mL). The mixture was stirred at 105 °C for 12 h. The amino functionalized MCM-48 silica 1 was collected by filtration, washed repeatedly with CH₂Cl₂, and dried under vacuum at 70 °C. Weight gain showed that 0.43 mmol of the aminopropyl moiety was immobilized on 1.0 g of MCM-48 silica 1.

2.4. Preparation of the MCM-48 supported 2-pyridinylmethanimine

To a stirred solution of 2-carboxypyridine (0.5 mmol) and Et₃N (0.5 mmol) in toluene (25 mL), 3-aminopropylated MCM-48 silica 1 (1 g, 0.43 mmol) was added. The mixture was stirred at 50 °C for 3 h. After filtration, the powder was washed several times with methylene chloride and dried under vacuum at 70 °C to give 3-aminopropylated MCM-48 silica supported pyridinylmethanimine 2. The weight gain showed that 0.38 mmol of 2-carboxypyridine was immobilized on 1.0 g of mesoporous MCM-48 silica 2.

2.5. Preparation of the MCM-48 supported Pd-catalyst 3

To a stirred solution of 2 (1 g, 0.38 mmol) in CH₂Cl₂ (25 mL), 0.3 mmol of PdCl₂ was added and stirred at 50 °C for 6 h. The MCM-48 supported Pd- catalyst was then collected by filtration and washed with CH₂Cl₂ and methanol. After drying in vacuo at 80 °C, the MCM-48 supported Pd-catalyst 3 was obtained as a reddish colored solid. The weight gain and ICP analyses showed that 0.26 mmol of Pd was immobilized onto 1.0 g of MCM-48 supported 3.

2.6. General procedure for the Heck reaction

All reactions were carried out in a 4 mL glass vial equipped with a Teflon screw cap. A mixture of aryl halide (1 mmol), olefin (1.2 mol equiv.), Na₂CO₃ (2 mol equiv.), and the Pd catalyst 3 (0.5 mg, 0.013 mol%, 130 mol ppm) in aqueous DMA (1 : 1) was stirred at 130 °C for 5 h, and monitored periodically by GC analysis. After the completion of the reaction, it was cooled at room temperature and diluted with EtOAc. The immobilized Pd-catalyst 3 was separated by filtration and washed with EtOAc. The organic layer was washed by H₂O, brine, dried over MgSO₄ and evaporated under reduced pressure. The residue was purified by short column chromatography on silica gel eluted with n-hexane/EtOAc, which afforded the desired coupling products in 82–96% isolated yields.

2.7. General procedure for the Suzuki reaction

A mixture of aryl halide (1 mmol), boronic acid (1.1 mol equiv.), K₂CO₃ (2 mol equiv.), and the Pd-catalyst 3 (0.013–0.025 mol%) in aqueous ethanol (1 : 1) was stirred at 90 °C for 5 h. The reaction was monitored using GC until the complete consumption of the aryl halide. The Pd-catalyst 3 was separated by filtration and the reaction mixture was diluted with H₂O and EtOAc. The organic layer was separated, dried over MgSO₄ and evaporated under reduced pressure. The residue was purified by short column chromatography on silica gel to give the corresponding coupling products in up to 96% yield.

2.8. General procedure for the Sonogashira reaction

Aryl halide (1 mmol), phenylacetylene (1.1 mol equiv.), piperidine (2 mol equiv.) and the Pd-catalyst 3 (0.013–0.025 mol%) was stirred at 80 °C for 4 h and the reaction progress was monitored periodically by GC analysis. The reaction mixture was cooled at room temperature and diluted with EtOAc and the immobilized Pd-catalyst was separated by filtration. The organic layer was washed by H₂O, dried over MgSO₄ and the solvent was evaporated under reduced pressure. The residue was purified by short column chromatography on silica gel eluted with n-hexane/EtOAc to afford the corresponding coupling products in up to 96% yield.

3. Results and discussion

3.1. Characterization of the MCM-48 supported Pd-catalyst 3

The immobilization of the Pd-catalyst onto nanostructured mesoporous MCM-48 silica was performed in three steps (Scheme 1). The treatment of MCM-48 silica with (3-aminopropyl)triethoxysilane in refluxing toluene gave aminopropylated silica gel 1 (0.43 mmol, (CH₂)₃NH₂/g). The loading ratio of the aminoproplylated moiety can be adjusted by changing the amount of (3-aminopropyl)triethoxysilane in the immobilization process. The ¹³C NMR indicates the bond formation between triethoxysilane and MCM-48 silica (Fig. 1c).

Scheme 1 Preparation of the MCM-48 supported heterogeneous Pd-catalyst 3.

Fig. 1 (a) TEM image of parent MCM-48; (b) TEM image of MCM-48 supported Pd-catalyst 3; (c) ¹³C NMR of MCM-48 supported 1; (d) XRD of MCM-48 and Pd-catalyst 3; (e) XPS and (f) EDX image of 3.

Reaction of 1 with 1.16 equiv. excess of 2-carboxypyridine in toluene at 50 °C afforded MCM-48 supported 2-pyridinylmethanimine 2 (0.38 mmol g⁻¹). The MCM-48 supported Pd-catalyst 3 was prepared by treatment of 2 with PdCl₂ in CH₂Cl₂ at 50 °C for 6 h. Based on the inductively coupled plasma (ICP) analysis, the loaded Pd content was 2.71% (0.26 mmol g⁻¹). The TEM images were obtained before (Fig. 1a) and after (Fig. 1b) modification of the MCM-48 silica. Both images showed that the hexagonal symmetry of the pore arrays is conserved after immobilization of the Pd-catalyst onto the MCM-48 silica. The 3D cubic structure and the pore arrays are conserved after the anchoring of the MCM-48 silica, which is also confirmed by XRD (Fig. 1d). The fresh MCM-48 shows a strong diffraction peak and five small diffraction peaks for the 211, 220, 321, 400, 420 and 332 planes. The presence of Pd 3d_3/2 (343 eV) and Pd 3d_5/2 (337 eV) peaks in the XPS image (Fig. 1e) suggested that the successful incorporation of the Pd(II) onto the MCM-48 supported Pd-catalyst 3. Moreover, the EDX image also revealed the presence of Pd-metal onto the Pd-catalyst 3. The presence of guest moieties on the mesoporous framework of MCM-48 resulted in the decrease of intensity of the peaks. However, the surface area, pore volume and pore size decreased due to the grafting of organic moieties onto the mesoporous MCM-48 silica (Table 1).

Table 1 Loading information of the MCM-48

Sample	Surface area (m^2 g^−1)	Pore diameter (nm)	Pore volume (cm^3 g^−1)	Functional group (mmol g^−1)
MCM-48	1250	3.25	0.71	—
1	865	2.82	0.62	0.43
2	790	2.35	0.48	0.38
3	465	2.12	0.35	0.26

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3.2. Mizoroki–Heck reaction

The prepared MCM-48 supported heterogeneous Pd-catalyst 3 was first used in the Mizoroki–Heck coupling reaction of iodobenzene. The coupling of iodobenzene with methyl acrylate in the presence of Na₂CO₃ in aqueous DMA with 0.1 mol% of 3 was initially studied as a model reaction, which delivered 99% conversion with 96% isolated yield of the product within 5 h without using any additive (Table 2, entry 1). The reaction conditions were then systematically optimized, and the results are presented in Table 2. The catalyst loading could be decreased even further from 0.013 to 0.01 mol% (130 to 100 mol ppm), where the catalyst still efficiently promoted the coupling reaction (entries 2 and 3). High conversion could be still maintained at 0.01 mol% of ultra-low Pd-catalyst loading (entry 3). Then, we surveyed this coupling reaction using 130 mol ppm of 3 by changing the solvents and bases. When the reaction was conducted in DMSO, NMP, and DMF instead of DMA, in the presence of different bases, similar results were obtained under the same reaction conditions (entries 4–10). In the presence of non-polar solvent octane, the reaction showed a slow conversion rate compared to the other polar solvents used (entry 11).

Table 2 Optimization of the Heck reaction^a

Entry	Solvent (1 : 1)	Base	3 (mol%)	Yield^b (%)
a All reactions were carried out using 1 mmol of iodobenzene, 1.2 mmol of methyl acrylate, a catalytic amount of 3 and 2 mmol of the base in 2 mL of solvent.b GC yield determined using n-dodecane as an internal standard and based on the amount of iodobenzene employed.c Isolated yield.
1	DMA : H2O	Na2CO3	0.1	99(96)^c
2	DMA : H2O	Na2CO3	0.013	98(95)^c
3	DMA : H2O	Na2CO3	0.01	86(82)^c
4	DMA : H2O	K2CO3	0.03	93
5	DMA : H2O	NaOMe	0.03	93
6	DMA : H2O	Na2PO4	0.03	94
7	DMA : H2O	K2PO4	0.03	92
8	DMSO : H2O	Na2CO3	0.03	91
9	NMP : H2O	Na2CO3	0.03	92
10	DMF : H2O	Na2CO3	0.03	93
11	Octane : H2O	Na2CO3	0.03	78

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The complex is very stable to oxygen and moisture; moreover, less change in its activity was observed when the Pd-catalyst was exposed to air and water in the Heck reaction. With these results in hand, several Heck couplings of aryl halides with different olefins were then tested, and the results are summarized in Table 3. Aryl iodides react with methyl, ethyl, butyl acrylate, isopropyl acrylamide, and styrene to give the corresponding coupling products in high yield. Excellent catalytic activity was observed in the couplings of deactivated iodotoluene, 4-iodoanisole (4b–h) as well as activated 4-chloroiodobenzene, 4-nitroiodobenzene, 4-iodoacetophenone and 4-trifluoromethyl iodobenzene with acrylates (4i–l). The deactivated aryl iodides possessing an electron-donating group showed a slight drop in reactivity compared to the activated aryl iodides possessing an electron-withdrawing group. The heterocyclic compound such as 3-iodopyridine efficiently promoted the coupling reaction to give the corresponding products (4m) in 92% yield. Moreover, the catalyst showed outstanding activity in the coupling of iodobenzene with isopropyl acrylamide and styrene to give the corresponding coupling products in up to 94% yield (4n–u).

Table 3 Heck reaction of aryl iodides with olefins using Pd-catalyst 3^a

a All reactions were carried out using 1 mmol of aryl iodide, 1.2 mol equiv. of olefin, 0.013 mol% of 3, and 2 mol equiv. of Na₂CO₃, in 2 mL of DMA/H₂O (1 : 1) at 130 °C for 5 h.

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The development of effective catalysts for the C–C bond formation of olefins with aryl bromides is highly important, since these are interesting substrates for industrial applications. Using diol-functionalized imidazolium ionic liquids along with PdCl₂, Cai et al.⁷² observed moderate yields in the Heck reaction of aryl bromides with various olefins, but the reaction rates were quite slow. By observing the promising catalytic activity of 3 for various aryl iodides, the catalyst was investigated for the coupling of aryl bromides with olefins. It was found that the catalyst showed outstanding activity in the coupling of aryl bromides with acrylates (Table 4, entries 4a–e, 4g and 4k). A catalyst loading of 0.04 mol% was sufficient to achieve high conversion within 5 h. Moreover, the catalyst also showed outstanding activity in the coupling of arylbromides with isopropyl acrylamide, and styrene smoothly afforded the corresponding coupling products in up to 90% yield (4o–q, 4s–u). Recently, R. Pleixats et al.⁷³ have reported hybrid silica materials, containing a di-(2-pyridyl)methylamine-palladium dichloride complex catalyzed (0.2 mol%) Heck reaction of activated aryl bromide (4-bromoacetophenone) with butyl acrylate in refluxing DMF, with significant decrease of catalytic activity (1^st run 100%, 4^th run 47% yield). Hence, our catalyst (0.04 mol%) showed better activity (1^st run 96%, 5^th run 83% yield) compared to their hybrid silica supported Pd-complex.

Table 4 Heck reaction of aryl bromides with olefins using Pd-catalyst 3^a

a All reactions were carried out using 1 mmol of aryl bromide, 1.2 mol equiv. of olefin, 0.04 mol% of 3, 2 mol equiv. of Na₂CO₃, in 2 mL of DMA/H₂O (1 : 1) at 130 °C for 5 h.

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3.3. Suzuki–Miyaura cross-coupling reaction

Heterogeneous silica-supported Pd-catalysts are extensively studied for the C–C bond formation reaction of aryl halides with aryl boronic acids, often referred to as the Suzuki–Miyaura cross-coupling reaction.⁷⁴ The properties of such Pd-catalysts can be tuned by ligands such as phosphines, amines, carbenes, dibenzylideneacetone, and imidazol-2-ylidenes.⁷⁵ The silica-immobilized N-heterocyclic carbine-Pd-complex has recently been reported as a catalyst for the Suzuki cross-coupling reaction.^76,77 Upon observing the high catalytic activity of MCM-48 supported Pd-catalyst 3 in the Heck reaction, we turned our attention to further testify our Pd-catalyst 3 for the Suzuki–Miyaura cross-coupling reaction. With the heterogeneous Pd-catalyst 3 (0.013 mol%) in hand, we then tested the Suzuki–Miyaura cross coupling reaction of 4-iodoanisole with phenylboronic acid in aqueous ethanol at 90 °C to for 5 h to give the corresponding biaryl product in 96% yield (Table 5, 5a). High catalytic activity was observed in the coupling of deactivated aryl iodides such as 4-iodotoluene, 4-iodophenol and 4-iodoaniline as well as activated 4-iodoacetophenone (5b–e). In order to investigate the scope of aryl halides in the coupling with phenylboronic acid, various aryl bromides were used in the coupling reaction. The coupling of activated or deactivated aryl bromides proceeded cleanly with 0.025 mol% of Pd to give the corresponding coupling product in up to 96% yield (5a–e). J. H. Clark⁷⁶ reported the pyridinyl functionalized silica gel supported Pd(OAc)₂ catalyzed (0.4 mol%) Suzuki–Miyaura cross-coupling reaction of aryl bromide in o-xylene at 110 °C under N₂ atmosphere. The reaction proceeded smoothly but the catalytic activity decreased (1^st run 1.5 h 100%, 4^th run 2.5 h 95% yield). Therefore, we used 0.025 mol% of the catalyst, which is sixteen times lower loading of the catalyst. Moreover, we performed this cross-coupling reaction under aqueous conditions at 90 °C with no significant loss of catalytic activity (1^st run, 5 h, 95%; 4^th run, 5 h, 87% yield).

Table 5 Suzuki–Miyaura coupling reaction with MCM-48 supported Pd-catalyst 3^a

a All reactions were carried out using aryl halide (1 mmol), Pd-catalyst 3 (0.013 mol% for aryl iodides, 0.025 mol% for aryl bromides), boronic acid (1.1 mol equiv.), K₂CO₃ (2 mol equiv.), EtOH/H₂O (1 : 1) at 90 °C for 5 h.

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3.4. Heterogeneous Sonogashira cross-coupling reaction

The Sonogashira cross-coupling of an aryl halide and a terminal alkyne is a useful tool for the synthesis of aryl-substituted acetylene compounds.⁷⁸ This method has been widely used for the synthesis of natural products,⁷⁹ biologically active molecules,⁸⁰ nonlinear optical materials and molecular electronics,⁸¹ dendrimeric and polymeric materials,⁸² macrocycles with acetylene links,⁸³ and polyalkynylated molecules.⁸⁴ With the heterogeneous Pd-catalyst 3 in hand, we investigated its catalytic activity towards the Sonogashira coupling reactions of various aryl halides with phenylacetylene in the presence of piperidine. The results are summarized in Table 6. The supported Pd-catalyst 3 with 0.013 mol% efficiently promoted the Sonogashira coupling reaction of aryl iodides under solvent and copper free reaction conditions within 4 h. It is worth to note that the catalytic activities (0.025 mol%) in the coupling of bromobenzene and substituted bromobenzenes were also excellent (6a–f). R. Pleixats et al.⁷³ reported hybrid silica materials containing a di-(2-pyridyl)methylamine-palladium dichloride complex catalyzed (0.2 mol%) Sonogashira cross-coupling reaction of 4-iodoanisole with phenylacetylene in refluxing DMF with significant decrease of catalytic activity (1^st run 100%, 5^th run 43% yield). Hence, we used 0.013 mol% of the catalyst, which is fifteen times lower loading of the catalyst. Moreover, we performed this cross-coupling reaction without the presence of copper salt under solvent free reaction conditions at 80 °C with no significant loss of catalytic activity (1^st run 95%, 5^th run 79% yield). Therefore, our catalyst showed better results compared to their report.

Table 6 SBA-16 supported Pd-catalyst 3 catalyzed Sonogashira reaction^a

a All reactions were carried out using 1 mmol of aryl halide, 1.2 mol equiv. of phenyl acetylene, Pd-catalyst 3 (0.013 mol% for aryl iodides, 0.025 mol% for aryl bromides), 2 mol equiv. of piperidine under solvent free reaction conditions at 80 °C for 4 h.

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4. Recycling of the catalyst

The recycling of the catalyst is an important issue in the heterogeneous catalysis system. Furthermore, we turn our attention to reuse our Pd-catalyst. The catalyst was used five times without a significant loss of its catalytic activity. The Pd-catalyst 3 was recovered and reused by the following steps: the reaction mixture was cooled to room temperature and diluted with EtOAc and filtered. The solid catalyst was washed with dichloromethane and dried at 80 °C under vacuum, and then used in the next run without changing of the reaction conditions.

After carrying out the reaction, the catalyst had consistent catalytic activity as shown in Table 7. Only slight a loss of catalytic activity was observed under the same reaction conditions as for the initial run. The slight loss of catalyst activity after five cycles was due to the loss of palladium from the support during reaction time (<0.16 mol ppm of Pd, ICP-AES). Thus, it is reasonable to believe that the immobilized catalyst can be repeatedly used for large-scale production without significant loss of its catalytic activity.

Table 7 Heck, Suzuki and Sonogashira reactions catalyzed by recycled Pd-catalyst 3

Cycle	Mizoroki–Heck yield^a (%)	Suzuki–Miyaura yield^b (%)	Sonogashira yield^c (%)
a Reaction was carried out according to Table 3, 4a using 0.5% of 3.b Reaction was carried out according to Table 5, 5b, X = I, using 0.5% of 3.c Reaction was carried out according to Table 6, 6a, X = I, using 0.5% of 3.
1	96	95	95
2	94	93	90
3	90	90	86
4	88	87	81
5	83 (<0.16 mol ppm Pd was leached out)	84	79

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5. Heterogeneity test

In order to check the heterogeneity of the Pd-catalyst 3, reactions were carried out in a similar manner as the general procedure for the Suzuki reaction (Table 5, 5a, X = I). After 52% conversion, the reaction mixture was filtered off under hot conditions and the aqueous solution was heated under identical reaction conditions for 2 h and GC analyzed for further conversions. No starting material was converted to the corresponding product after removal of the catalyst (Fig. 2). This experiment indicates that the Suzuki–Miyaura reactions followed a heterogeneous pathway.

Fig. 2 Hot filtration test of the Suzuki–Miyaura reaction (Table 5, 5f).

6. Conclusions

In conclusion, we have developed nanostructured MCM-48 supported Pd-catalyst 3 for Mizoroki–Heck, Suzuki–Miyaura and Sonogashira cross coupling reactions. The heterogeneous Pd-catalyst was found to be highly active for the coupling reactions of aryl iodide and bromide under aqueous conditions. The Sonogashira cross coupling reaction was performed under copper and solvent-free reaction conditions. Furthermore, this catalytic system was simply recovered and reused several times without a significant loss of its activity.

Acknowledgements

This study was supported by the Ministry of Education Malaysia, fund no. RDU140124. The authors are grateful to Professor Myung-Jong Jin, Inha University, South Korea and Professor Yasuhiro Uozumi, RIKEN, Wako, Japan for giving us valuable guidelines in this study.

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Footnote

† Electronic supplementary information (ESI) available: Experimental detail and NMR data of the coupling products. See DOI: 10.1039/c4ra16677a

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