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Article

Highly Efficient and Sustainable HT@NC/Pd Catalysts for Suzuki Coupling and Their Application in Elacestrant Synthesis

by
Jiajun He
1,†,
Muwei Liu
2,†,
Chao Chen
2,*,
Guozhang Li
2,
Kai Zheng
1 and
Chao Shen
1,2,*
1
College of Petroleum Chemical Industry, Changzhou University, Changzhou 213164, China
2
Zhejiang Collaborative Innovation Center for Full-Process Monitoring and Green Governance of Emerging Contaminants, College of Biology and Environmental Engineering, Zhejiang Shuren University, Hangzhou 310015, China
*
Authors to whom correspondence should be addressed.
†
These authors contributed equally to this work.
Catalysts 2025, 15(4), 389; https://doi.org/10.3390/catal15040389
Submission received: 12 March 2025 / Revised: 8 April 2025 / Accepted: 11 April 2025 / Published: 17 April 2025
(This article belongs to the Special Issue Sustainable Catalysis for Green Chemistry and Energy Transition)
Browse Figures
Versions Notes

Abstract

:
Mg-Al hydrotalcite (HT), comprising Mg2+ and Al3+ as layered hydroxide cations, was synthesized via a hydrothermal process at 200 °C. The HT was evaluated as a carrier, and subsequently, palladium was immobilized on the surface of the hydrotalcite (HT/NC), resulting in the development of an innovative biomass-based palladium catalyst. The catalyst underwent analysis by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). It exhibited remarkable catalytic efficiency and superior activity as a catalyst in the Suzuki–Miyaura coupling reaction in water. The catalyst was recyclable without a decline in activity and could be utilized more than 10 times, with exceptional yield. Furthermore, the commercially accessible anticancer drug Elacestrant can be readily produced using this protocol.

Graphical Abstract

1. Introduction

The palladium-catalyzed carbon–carbon coupling (Suzuki reaction) between aryl halides and phenylboronic acid is a significant process in contemporary chemical synthesis [1]. A multitude of extremely active homogeneous palladium catalysts have been examined for this process. The employment of homogeneous Pd catalysts requires significant expenses owing to the use of non-recoverable noble metals and ligands. Moreover, practical limitations such as the catalyst’s efficacy, reusability, and the separation of the catalyst from products limit the advantages of homogeneous Pd catalysts for many commercial applications [2]. Conversely, a heterogeneous Pd catalyst could overcome these limitations and offer a significant alternative technology [3].
In recent decades, nanoparticles of palladium supported with different substrates, including activated carbon materials [4], silica [5], polymers [6], magnetite nanoparticles [7], and metal oxides [8], have been developed and utilized for the Suzuki coupling reaction. Nonetheless, these techniques typically demand elevated catalyst loadings, high reaction temperatures, and extended reaction times. Hydrotalcite (HT) possesses a distinctive layered architecture and an abundance of surface hydroxyl groups, significantly enhancing its hydrophilicity [9,10]. The augmented contact area between the hydroxyl groups and metal ions on the surface of HT enhances the dispersion and stability of the active metal. Consequently, HT is a useful substrate for catalyst preparation. Dong et al. documented the Suzuki coupling reaction facilitated by a Pd–Co nanocatalyst supported on Mg–Fe–CHT [11]. Ruiz’s group described palladium based on hydrotalcite, which was the catalyst in the Suzuki coupling reaction [12]. However, these catalysts exhibited poorer catalytic stability.
Efficiency and environmental sustainability are essential concerns in modern organic chemistry [13,14,15,16,17,18,19,20,21,22,23,24,25,26]. Biomass-derived heterogeneous catalysts have exceptional stability. Our group has reported numerous organic reactions with biomass-based heterogeneous catalysts in recent years [27,28,29,30,31,32,33,34,35]. These biomass catalysts have the advantages of being highly efficient and cost-effective and requiring a simple preparation process [36,37]. Hence, we developed a recyclable HT@NC/Pd catalyst for the Suzuki coupling reaction of aryl halides with aryl boric acid in water. The catalyst can be easily separated from the reaction system by the method of filtration and can be reused at least 10 times with excellent yield.

2. Results and Discussion

HT@NC/Pd was synthesized by a three-step process (Scheme 1). Firstly, the Mg-Al hydrotalcite precursor was synthesized from 2.41 g of AlCl3·6H2O, 3.81 g of MgCl2, 16.0 g of NaOH, and 15.90 g of Na2CO3 at 75 °C [38]. Thereafter, the HT and glycosamine mixture was subjected to sonication in water. The combination was hydrothermally deposited into HT at 200 °C to yield HT@NC. PdCl2 and HT@NC were subsequently introduced to ethanol and agitated at 60 °C. The combination was further reduced using sodium borohydride to yield Pd(0) particles, resulting in the sample HT@NC/Pd.
The electronic characteristics of the HT@NC/Pd catalyst were examined by XPS analysis (Figure 1). The HT@NC/Pd(0) exhibits binding energies of 335.0 eV for Pd 3d3/2 and 340.3 eV for Pd 3d5/2, which is indicative of Pd(0). This indicates that the absorbed Pd(II) was efficiently converted to Pd(0) particles by sodium borohydride. Conversely, the HT@NC/Pd(II) displays binding energies of 337.4 eV for Pd 3d3/2 and 342.3 eV for Pd 3d5/2, which is indicative of Pd(II), demonstrating that ultrasonication alone was insufficient to decrease the absorbed Pd(II) to Pd(0) particles [39].
The XRD pattern of the Mg-Al hydrotalcite (Figure 2) displays seven different diffraction peaks at 11.7°, 23.5°, 35.0°, 39.7°, 47.2°, 61.1°, and 62.5°, corresponding to the (003), (006), (009), (015), (018), (110), and (113) crystal planes, respectively. Both the HT@NC and HT@NC/Pd composites exhibit diffraction patterns that are akin to the virgin HT material, with supplementary distinctive peaks at 2θ = 40°, 47°, and 68°, which is indicative of metallic palladium. These observations validate the effective deposition and reduction of Pd(0) particles on the hydrotalcite substrate.
HT/NC@Pd was identified by SEM micrographs and EDS spectra (Figure 3). The photos distinctly illustrate the stratified architecture of the catalyst, which is characteristic of a lamellar hydrotalcite morphology with an uneven configuration. The energy spectrum analysis photos of HT/NC@Pd indicate that the catalyst was effectively doped with biomass carbon and metal palladium. The real palladium content of the catalyst was measured by ICP elemental analysis, and it was found to be 2.38 wt%.
The catalytic efficacy was assessed via the Suzuki–Miyaura coupling reaction involving iodobenzene (1a) and phenylboric acid (2a) in an aqueous environment. A systematic optimization of reaction parameters, such as the temperature, catalyst dosage, and reaction time, was performed to determine the optimal conditions. No detectable coupling product (3a) was observed when the reaction was performed in the absence of a Pd catalyst (Table 1, entries 1–3). Notably, compared to HT/Pd, HT@NC/Pd exhibited greater catalytic capacity (Table 1, entries 4, 5). Subsequently, various bases, including K2CO3, NaOH, Na2CO3, KOH, K3PO4, Et3N, and Cs2CO3, were evaluated for their influence on the reaction (Table 1, entries 5–11). The optimal yield was achieved with the utilization of KOH. The investigation of varying temperatures revealed that 90 °C was optimal for the Suzuki coupling, providing the greatest yield of 96% (Table 1, entries 6, 12–15). Ultimately, augmenting the catalyst dosage and extending the reaction time did not enhance the yield of 3a (Table 1, entries 16, 17). When the amount of the catalyst was reduced to 5 mg and 1 mg, the yields decreased significantly (Table 1, entries 18, 19).
After determining suitable reaction conditions, the substrate scope was thoroughly investigated utilizing diverse aryl halides and aryl boronic acids. The preliminary experiments concentrated on phenylboronic acid in conjunction with other aryl iodides. Electron-withdrawing substituents (Table 2, 3e–3i) on the aryl iodide often produced superior yields in comparison to electron-donating groups (Table 2, 3b–3d). Notably, ortho-substituted and meta-substituted derivatives exhibited lower reactivity than their para-substituted counterparts (Table 2, 3b, 3e, 3h, 3k, 3l, 3m) [35]. The impact of steric hindrance and electronic effects was proposed. Subsequent investigations encompassed aryl bromides and chlorides, revealing effective coupling with phenylboronic acid for brominated substrates (Table 2, 3a, 3n–3q), whereas the chlorinated compounds produced moderate outputs (Table 2, 3a, 3b). Moreover, heteroaryl bromides exhibited superior coupling efficiency with aryl boronic acid, attaining good yields under the optimum conditions (Table 2, 3r–3t).
Our research strategy focused on the production of essential intermediates for Elacestrant, a novel selective estrogen receptor degrader (SERD) exhibiting remarkable efficacy in targeted breast cancer treatment (Scheme 2) [40,41]. Amino-palladium coordination complexes present considerable difficulties in the elimination of leftover palladium from intermediates. To resolve this issue, we utilized HT@NC/Pd as the catalyst for the coupling reaction between ELA-7 and ELC-7 in an aqueous medium at 90 °C for 6 h, resulting in effective conversion. The gram-scale synthesis of the Elacestrant intermediate EL-1 exhibited remarkable purity (>99%), an insignificant palladium concentration (<10 ppm), and a substantial overall yield (95%).
The catalytic stability of HT@NC/Pd was assessed via consecutive recycling investigations of the Suzuki coupling reaction in water. After each catalytic cycle, the catalyst was taken back and subsequently utilized in consequent reactions. Remarkably, the catalyst exhibited stable catalytic efficiency during ten consecutive cycles, frequently achieving product yields of 95%, as demonstrated in Figure 4. These results highlight the remarkable stability and reusability of the HT@NC/Pd catalyst.

3. Experimental Materials

The starting material was commercially available and could be used without further purification. Aluminum chloride hexahydrate (AlCl3·6H2O) and magnesium chloride (MgCl2) were supplied by Dongtai Yongtai Chemical Co., LTD. (Dongying City, Shandong Province, China). Glycoamine was from Shanghai Darui Fine Chemical Co., LTD. (Shanghai, China). Anhydrous sodium carbonate was supplied by Wenzhou Chemical Materials Factory. Sodium hydroxide was supplied by Shanghai Lingfeng Chemical Reagent Co., LTD. (Shanghai, China). Palladium chloride (PdCl2, 59.5%) was supplied by Shanghai J&K Science Co., LTD. (Shanghai, China) Other materials were analytical-grade and used after receipt. All compounds were subjected to column chromatography, using different eluent mixtures. These compounds were also purified and characterized, and the spectral data were in accordance with the literature data. Copies of 1H and 13C NMR spectra are given in the Supplementary Information File.

3.1. Preparation of HT Particles

HT particles were synthesized via a coprecipitation method [42]. Initially, a saline solution was prepared by dissolving 2.41 g of AlCl3·6H2O and 3.81 g of MgCl2 in 100 mL of deionized water under magnetic stirring. Simultaneously, a precipitating agent was obtained by dissolving 16.0 g of NaOH and 15.9 g of Na2CO3 in 100 mL of deionized water. The salt solution was then transferred to a three-neck flask and maintained at 75 °C in an electric thermostatic water bath. The precipitating agent was gradually added at a controlled rate of 30 drops per minute using an automatic burette. The resulting solid was calcined at 450 °C for 4 h under a nitrogen atmosphere, followed by hydration with deionized water and a 2 h standing period. The final product was isolated through filtration, yielding a white solid that was dried at 70 °C for 24 h.

3.2. Preparation of HT/Pd Particles

HT/Pd was synthesized through a modified reduction method [43]. Briefly, 0.95 g of hydrotalcite was dispersed in 40 mL of ethanol via 30 min sonication. Subsequently, 50 mg of PdCl2 was introduced into the suspension and subjected to further sonication for 1 h. Following this, 85 mg of NaBH4 was added as a reducing agent, and the mixture was maintained at 60 °C with continuous stirring for 2 h. The resulting black precipitate was collected through vacuum filtration, thoroughly washed with deionized water and ethanol, and finally vacuum-dried at 70 °C for 24 h.

3.3. Preparation of HT@NC Particles

HT@NC was synthesized following a modified hydrothermal method [44]. Initially, 0.8 g of HT particles was dispersed in a 30 mL aqueous solution containing 0.04 g of glucosamine hydrochloride through 0.5 h sonication. The pH of the suspension was then adjusted to 10–11 with an ammonia solution and transferred to a tetrafluoroethylene-lined stainless steel autoclave. Hydrothermal treatment was conducted at 200 °C for 12 h. The resulting product was isolated by filtration, sequentially washed with water and ethanol, and vacuum-dried at 70 °C for 24 h.

3.4. Preparation of HT@NC/Pd Catalyst

HT@NC/Pd was synthesized following a previously reported protocol [45]. Briefly, 0.95 g of HT@NC support was dispersed in 40 mL of ethanol via 0.5 h sonication. Subsequently, 50 mg of palladium chloride was introduced into the suspension, followed by additional sonication for 1 h. The reduction process was initiated by adding 85 mg of NaBH4, and the mixture was vigorously stirred at 60 °C for 2 h. The resulting black precipitate was isolated through filtration, thoroughly washed with ethanol, and vacuum-dried at 70 °C for 24 h.

3.5. General Procedure for the Suzuki Coupling Reactions

The reaction mixture, containing aryl halides (1.0 mmol), aryl boronic acid (1.5 mmol), HT@NC/Pd (10 mg), and water (3 mL) was stirred at an ambient temperature under atmospheric conditions. Following completion, the mixture underwent extraction with ethyl acetate, followed by drying over anhydrous magnesium sulfate, filtration, and vacuum concentration. The crude material was subsequently purified through silica gel column chromatography using petroleum ether/ethyl acetate (100:1) as the eluent system.

3.6. General Procedure for Catalyst Recovery

The reaction system, comprising iodobenzene (1.0 mmol), phenyl boronic acid (1.5 mmol), and HT@NC/Pd (10 mg) in water (3 mL) was stirred at an ambient temperature. Upon reaction completion, the catalyst was recovered through filtration, sequentially washed with water and ethanol (3 × 2 mL each), and vacuum-dried for subsequent reuse.

4. Conclusions

In conclusion, the Mg-Al hydrotalcite (HT) was synthesized via a hydrothermal process at 200 °C and was evaluated as a carrier; subsequently, palladium was immobilized on the surface of the hydrotalcite, resulting in the development of an innovative biomass-based palladium catalyst. The catalysts underwent analysis by XRD, SEM, and XPS spectra. The synthesized HT@NC/Pd catalyst exhibited outstanding catalytic efficacy in Suzuki coupling processes involving various aryl boronic acids and aryl halides. The catalyst demonstrated exceptional recyclability, sustaining high activity over 10 successive cycles in water and enabling straightforward recovery through filtration. Furthermore, this catalytic was especially successful in synthesizing the commercially important medicinal drug Elacestrant.

Supplementary Materials

The following supporting information can be downloaded at https://www.mdpi.com/article/10.3390/catal15040389/s1: Topic S1: General Information; Topic S2: Experimental Section; Topic S3: Characterization of Products; Topic S4: 1H and 13C NMR Spectra of the Compounds. References [35,42,43,44,45,46,47] are cited in the Supplementary Materials.

Author Contributions

Conceptualization, C.S. and C.C.; Investigation, J.H. and M.L.; Supervision, C.S.; Writing—original draft, G.L. and K.Z. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by the Key Research & Development Project of Science Technology Department of Zhejiang Province (No. 2024C01203), the Zhejiang Shuren University Basic Scientific Research Special Funds.

Data Availability Statement

The original contributions presented in this study are included in the article/supplementary material. Further inquiries can be directed to the corresponding authors.

Conflicts of Interest

The authors declare no conflicts of interest.

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Catalysts 15 00389 sch001
Scheme 1. Synthesis of HT@C/Pd and HT@NC/Pd catalysts.
Scheme 1. Synthesis of HT@C/Pd and HT@NC/Pd catalysts.
Catalysts 15 00389 sch001
Catalysts 15 00389 g001
Figure 1. XPS spectra of HT@NC/Pd(0) catalyst and HT@NC/Pd(II) catalyst.
Figure 1. XPS spectra of HT@NC/Pd(0) catalyst and HT@NC/Pd(II) catalyst.
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Catalysts 15 00389 g002
Figure 2. XRD spectra of HT, HT@NC, and HT@NC/Pd catalysts.
Figure 2. XRD spectra of HT, HT@NC, and HT@NC/Pd catalysts.
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Figure 3. SEM and EDS images of HT@NC/Pd catalyst.
Figure 3. SEM and EDS images of HT@NC/Pd catalyst.
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Scheme 2. Application of the catalyst in the gram-scale synthesis of Elacestrant intermediate.
Scheme 2. Application of the catalyst in the gram-scale synthesis of Elacestrant intermediate.
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Figure 4. Recycling and reuse of HT@NC/Pd in the Suzuki coupling.
Figure 4. Recycling and reuse of HT@NC/Pd in the Suzuki coupling.
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Table 1. Optimization of reaction conditions a.
Table 1. Optimization of reaction conditions a.
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EntryCatalystBaseTemp (°C)Time (h)Yield b(%)
1-K2CO3900.5-
2HTK2CO3900.5-
3HT@NCK2CO3900.5-
4HT/PdK2CO3900.595
5HT@NC/PdK2CO3900.593
6HT@NC/PdKOH900.596
7HT@NC/PdK3PO4900.592
8HT@NC/PdNaOH900.594
9HT@NC/PdNa2CO3900.592
10HT@NC/PdEt3N900.571
11HT@NC/PdCs2CO3900.583
12HT@NC/PdKOHrt0.566
13HT@NC/PdKOH500.575
14HT@NC/PdKOH700.590
15HT@NC/PdKOH1000.595
16HT@NC/PdKOH900.595 c
17HT@NC/PdKOH90196
18HT@NC/PdKOH900.572 d
19HT@NC/PdKOH900.537 e
a Reaction conditions: Aryl halide 1a (1 mmol), aryl boronic acid 2a (1.5 mmol), HT@NC/Pd catalyst (10 mg) and base (1.5 mmol), and 3 mL of water in air. b Isolated yield. c 20 mg catalysts. d 5 mg catalysts. e 1 mg catalysts.
Table 2. Suzuki coupling between aryl halides and aryl boronic acids in the presence of HT@NC/Pd a,b.
Table 2. Suzuki coupling between aryl halides and aryl boronic acids in the presence of HT@NC/Pd a,b.
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Catalysts 15 00389 i003
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Catalysts 15 00389 i006
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a Reaction conditions: aryl halide 1 (1 mmol), aryl boronic acid 2 (1.5 mmol), HT@NC/Pd catalyst (10 mg) and base (1.5 mmol), and 3 mL of water in the air. b Isolated yield.
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He, J.; Liu, M.; Chen, C.; Li, G.; Zheng, K.; Shen, C. Highly Efficient and Sustainable HT@NC/Pd Catalysts for Suzuki Coupling and Their Application in Elacestrant Synthesis. Catalysts 2025, 15, 389. https://doi.org/10.3390/catal15040389

AMA Style

He J, Liu M, Chen C, Li G, Zheng K, Shen C. Highly Efficient and Sustainable HT@NC/Pd Catalysts for Suzuki Coupling and Their Application in Elacestrant Synthesis. Catalysts. 2025; 15(4):389. https://doi.org/10.3390/catal15040389

Chicago/Turabian Style

He, Jiajun, Muwei Liu, Chao Chen, Guozhang Li, Kai Zheng, and Chao Shen. 2025. "Highly Efficient and Sustainable HT@NC/Pd Catalysts for Suzuki Coupling and Their Application in Elacestrant Synthesis" Catalysts 15, no. 4: 389. https://doi.org/10.3390/catal15040389

APA Style

He, J., Liu, M., Chen, C., Li, G., Zheng, K., & Shen, C. (2025). Highly Efficient and Sustainable HT@NC/Pd Catalysts for Suzuki Coupling and Their Application in Elacestrant Synthesis. Catalysts, 15(4), 389. https://doi.org/10.3390/catal15040389

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