Next Article in Journal
Selective Supercritical CO2 Extraction and Biocatalytic Valorization of Cucurbita pepo L. Industrial Residuals
Next Article in Special Issue
N-Rich, Polyphenolic Porous Organic Polymer and Its In Vitro Anticancer Activity on Colorectal Cancer
Previous Article in Journal
Structural and Functional Analysis of the Pyridoxal Phosphate Homeostasis Protein YggS from Fusobacterium nucleatum
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Molecules
Volume 27
Issue 15
10.3390/molecules27154777
molecules-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Palladium Supported on Porous Organic Polymer as Heterogeneous and Recyclable Catalyst for Cross Coupling Reaction

by
Guanying Shi
1 and
Zhenhua Dong
2,*
1
Institute of Agricultural Products Processing, Henan Academy of Agricultural Sciences, Zhengzhou 450002, China
2
College of Chemistry and Chemical Engineering, Henan University of Technology, Lianhua Street 100, Zhengzhou 450001, China
*
Author to whom correspondence should be addressed.
Molecules 2022, 27(15), 4777; https://doi.org/10.3390/molecules27154777
Submission received: 6 July 2022 / Revised: 22 July 2022 / Accepted: 25 July 2022 / Published: 26 July 2022
(This article belongs to the Special Issue Porous Polymer Materials: Design & Applications)
Browse Figures
Versions Notes

Abstract

:
Palladium immobilized on an amide and ether functionalized porous organic polymer (Pd@AEPOP) is reported to be an effective heterogeneous catalyst for the Heck cross-coupling reaction of aryl iodides with styrene for the synthesis of diphenylethene derivatives. Excellent yields can be obtained using a 0.8 mol% Pd catalyst loading under the optimized reaction condition. The heterogeneous Pd@AEPOP catalyst can also be applied on the Suzuki reaction and the reduction of nitroarene.

1. Introduction

As Nobel reactions, the Suzuki reaction and Heck reaction have a wide range of applications in organic synthetic chemistry [1,2,3,4]. The bi-aryl products are multipurpose building blocks in pharmaceuticals, agrochemicals and semiconductor materials such as organic light emitting diodes [5]. The cross-coupling reaction is one of the most important methods for the direct synthesis of related products [6]. In the past decades, a wide range of coupling reactions has been catalyzed effectively by palladium catalysts to form the carbon–carbon bond [7,8,9,10,11,12,13]. In order to reduce the reaction cost and expand the catalytic application, several metals have displayed analogous catalytic ability in this transformation [14]. Except for the noble metals, such as Au [15,16], Ru [17], Pt [18] and Ag [19], the low-cost transition metals, such as Cu [20], Ni [21], Co [22] and Fe [23], have also been investigated by chemists. However, compared with the Pd catalyst, other metal catalyzed coupling reactions still have many disadvantages, such as the low catalyst utilization rate, the ligands with complex structures, and the limited range of substrate scopes. The Pd-catalyzed coupling reactions are still the most popular research. However, palladium has a number of drawbacks, such as it being expensive, sensitive to air and moisture, and difficult to recover.
In order to improve the catalytic efficiency of Pd, remarkable research has been accomplished. Among this research, nano-catalysis is an emerging method [24,25,26,27,28]. Recently, considerable attention has been paid to the Pd nanoparticles (NPs). Several Pd nano-catalysts have displayed outstanding catalytic activity in cross-coupling reactions [29,30,31,32]. Existing studies indicated that the catalytic activity of Pd NPs is related to their intrinsic shape and size [33]. Hence, it is very important to confine the growth of NPs and control the size of NPs. However, due to the high surface energy, narrow sized metal particles tend to aggregate. It remains a standing challenge to obtain stable Pd NPs with a narrow size and thus outstanding catalytic activity. In our previous studies, we reported several porous organic polymers with diverse linked groups and well-defined pore structures [34,35,36]. In order to continue our efforts to extend the catalytic application of heterogeneous Pd NP catalysts, herein, we report a Pd NP supported on an amide and ether functionalized porous organic polymer (Pd@AEPOP) as an efficient and recyclable catalyst for Heck and Suzuki coupling.

2. Results and Discussion

The synthetic method of Pd@AEPOP is shown in Scheme 1. The typical synthesis for AEPOP was described in the previous report [37]. Subsequently, the supported Pd nanoparticles’ (NPs) catalyst, named Pd@AEPOP, is prepared by mixing AEPOP with H2PdCl4 with reduction by NaBH4. The Pd content is 4.38% from ICP (inductively coupled plasma) analysis.
Though the characterization of APOP has been well indicated. The molecular structure of AEPOP is also confirmed by the 13C CP-MAS solid state NMR spectrum. As shown in Figure 1, the characteristic resonance signals at 232.25, 165.83, 155.92, 133.39 and 121.83 ppm are observed. The signal at 232.25 corresponds to the carbonyl carbon, whereas the four strong signals that appeared from 165.83 to 121.83 ppm may originate from the four different aromatic carbons.
The porosity and morphology of AEPOP was described by SEM. As shown in Figure 2a, it is clear that AEPOP has a coralline-like morphology. The aperture in the surface can accommodate the Pd particles. The HR-TEM analysis shown in Figure 2b–f provides the morphology and shape of Pd@AEPOP. Figure 2b give the dispersity of Pd NPs at a large scale (50 nm). The dispersibility is unsatisfactory, and it looks like the Pd particles agglomerate. However, the enlarged photo, Figure 2c, shows that the Pd particles are separated from each other. According to the statistics regarding the Pd particles, an average particle size of approximately 5–8 nm is observed. Figure 2d,e show the clear morphology and the shape of Pd NPs with enlarged images (5 nm). It is clear that the Pd particles are nanoparticles. The diffraction fringe of Pd is clearly visible from Figure 2f in the red pane. The boundary is distinct between the two different Pd particles.
Then the structural regularity and crystalline nature of Pd@AEPOP was determined by powder PXRD analysis. The PXRD pattern of Pd@AEPOP (blue line) gives new small peaks at 2θ values 39.84 and 45.88 as shown in Figure 3. The values can be assigned to the refractions of (111) and (200) of Pd NPs, respectively.
The Pd@AEPOP was also confirmed by FTIR spectroscopy. As shown in Figure S1 in the Supplementary Materials, the IR spectroscopy of Pd@AEPOP (blue line) has no obvious change compared with AEPOP (red line). However, the Pd content is higher than that in our previous work. The results indicate that the Pd NPs may be embedded into the porous material by physical absorption.
In order to evaluate the catalytic activity of the Pd@AEPOP catalyst for cross-coupling reactions, the Heck reaction of 4-methyl iodobenzene with styrene is selected as the model reaction. Several conditions are examined for the Heck reaction, and the results are summarized in Table 1. Using 20 mg of the Pd@AEPOP catalyst, the screening of the solvents reveals that DMF is the best solvent with a 40% yield (entries 1–4). Then various bases were tested (entries 5, 6). The organic base Et3N is found to be the best base with a 55% yield. Then a 99% yield can be achieved by the screening of temperature, at 120 °C (entry 9). The best yield of 95% is obtained by prolonging the reaction time to 10 h (entry 10).
With the optimized reaction conditions in hand, various substitutional aryl iodides were tested and the results are summarized in Table 2. Using styrene as a standard substance, an excellent yield can be achieved for different aryl iodides containing both electron-donating (Me, tBu) and electron-withdrawing (Cl) groups (Table 2, entries 1–4). Then the ethylacrylate is also used as a standard substance, and various substitutional aryl iodides also give excellent yields (Table 2, entries 5–11). The aryl bromide and chloride substrates were also extended. Unfortunately, no products were observed.
Then the recyclability of the Pd@AEPOP catalyst is tested. After the end of the model reaction, the Pd@AEPOP was separated by simple centrifugation. Then the catalyst was used for the next catalysis after washing by DMF and drying. As shown in Scheme 2, the catalyst can be recycled nine times. The decrease in activity may result from the loss of the Pd in the recycling processes. Hence, we also carried out the ICP analysis for the final Pd@AEPOP catalyst after the tenth use and the Pd content was 3.96%. In view of the possible physical adsorption of Pd particles on the porous organic polymer, the results of recyclability are satisfactory.
Most existing reports about Pd NPs’ catalysis focus mainly on the Suzuki cross-coupling reaction. Hence, the performance of the Pd@AEPOP catalyst for the Suzuki reaction is investigated, and the results are shown in Scheme 3. Under the standard condition in this paper, a 99% yield is obtained (condition 1). The Suzuki reaction also proceeds under more the mild and eco-friendly condition 2 using water as a solvent. The Pd@AEPOP catalyst can also be applied for the reduction of nitroarenes using NaBH4 as a reductant with 99% yield.

3. Experimental Section

3.1. Materials

The amide and ether functionalized porous organic polymer was prepared via the reaction of 4,4′-diaminodiphenyl ether with 1,3,5-benzenetricarbonyl chloride. The AEPOP was well characterized in our previous report.

3.2. Synthesis of Pd@AEPOP

In total, 10 mL of H2PdCl4 (12 mg Pd/mL) was added to the mixture of 2 g AEPOP with 300 mL H2O under stirring at room temperature. The reaction was stirred for 24 h. Then a solution of 856 mg NaBH4 in 100 mL H2O was added to the reaction slowly. The resulted mixture was stirred for 12 h at room temperature. Finally, the solid was filtered and washed by MeOH and water three times. The product was dried under vacuum at 130 °C for further use.

3.3. General Procedure for Heck Reaction

Solutions of 20 mg Pd@AEPOP, 1 mmol iodobenzene, 1.2 mmol styrene, 1.5 mmol Et3N were mixed with 2 mL DMF in glass tube. Then the reaction was carried by 120 °C for 10 h. After reaction, the mixture was cooled and extracted with 20 mL diethyl ether three times. The combined organic layer was dried (Na2SO4) and concentrated to give crude product. The desired product was purified by flash column chromatography on silica gel (petroleum ether and ethyl acetate).

3.4. General Procedure for Recycling Experiment

Solutions of 20 mg Pd@AEPOP, 1 mmol iodobenzene, 1.2 mmol styrene, 1.5 mmol Et3N were mixed with 2 mL DMF in glass tube (Scheme 2). Then the reaction was carried out at 12 °C for 10 h. After the reaction, the solid was separated by centrifugation. The liquid was further processed according to Section 3.3 to obtain the yield. The solid was washed by DMF and dried. Then the reclaimed catalyst was reused next time.

3.5. General Procedure for Suzuki Reaction

Condition 1: 20 mg Pd@AEPOP, 1 mmol iodobenzene, 1.5 mmol arylboronic acids, and 1.5 mmol Et3N were mixed in 2.0 mL DMF in glass tube (Scheme 3). Then the reaction was carried out at 120 °C for 10 h. After reaction, the mixture was cooled and extracted with 20 mL diethyl ether three times. The combined organic layer was dried (Na2SO4) and concentrated to give crude product. The desired product was purified by flash column chromatography on silica gel (petroleum ether).
Condition 2: 10 mg Pd@AEPOP, 1 mmol iodobenzene, 1.5 mmol arylboronic acids, and 2 mmol K2CO3 were mixed in 2.0 mL water in glass tube (Scheme 3). Then the reaction was carried out at 80 °C for 1 h. After reaction, the mixture was cooled and extracted with 20 mL diethyl ether three times. The combined organic layer was dried (Na2SO4) and concentrated to give crude product. The desired product was purified by flash column chromatography on silica gel (petroleum ether).

3.6. General Procedure for Reduction of Nitroarene

Solutions of 10 mg Pd@AEPOP, 1 mmol nitroarenes were mixed with 2.0 mL water. Then 5 mmol NaBH4 was added to the reaction slowly (Scheme 3). Then the reaction was stirred 30 min at room temperature. The reaction was extracted with 20 mL diethyl ether three times. The combined organic layer was dried (Na2SO4) and concentrated to give crude product. The desired product was purified by flash column chromatography on silica gel (petroleum ether and ethyl acetate).

4. Conclusions

In conclusion, an efficient method for the Heck cross-coupling reaction of aryl iodides with styrene for the synthesis of a di-aryl ethene derivative using Pd@AEPOP as an active and reusable catalyst has been developed. Under optimized reaction conditions, an excellent yield was achieved by a 0.8 mol% palladium catalyst loading. The Pd catalyst can be recycled nine times without an obvious decrease in activity. Moreover, the catalyst can also be applied for the Suzuki reaction and reduction of nitroarene.

Supplementary Materials

The following are available online at https://www.mdpi.com/article/10.3390/molecules27154777/s1, Figure S1: FT-IR spectra of AEPOP and Pd@AEPOP.

Author Contributions

Conceptualization and investigation, G.S.; writing—original draft preparation, writing—review and editing, Z.D. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are available in insert article or Supplementary Materials here.

Acknowledgments

The authors are grateful to the Innovative Funds Plan of Henan University of Technology (No. 2020ZKCJ29) and the Cultivation Programme for Young Backbone Teachers in Henan University of Technology. All individuals included in this section have consented to the acknowledgement.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Vásquez-Céspedes, S.; Betori, R.C.; Cismesia, M.A.; Kirsch, J.K.; Yang, Q. Heterogeneous Catalysis for Cross-Coupling Reactions: An Underutilized Powerful and Sustainable Tool in the Fine Chemical Industry? Org. Process Res. Dev. 2021, 25, 740–753. [Google Scholar] [CrossRef]
  2. Kadu, B.S. Suzuki–Miyaura cross coupling reaction: Recent advancements in catalysis and organic synthesis. Catal. Sci. Technol. 2021, 11, 1186–1221. [Google Scholar] [CrossRef]
  3. Sherwood, J.; Clark, J.H.; Fairlamb, I.J.S.; Slattery, J.M. Solvent effects in palladium catalysed cross-coupling reactions. Green Chem. 2019, 21, 2164–2213. [Google Scholar] [CrossRef] [Green Version]
  4. Hooshmand, S.E.; Heidari, B.; Sedghi, R.; Varma, R.S. Recent advances in the Suzuki-Miyaura cross-coupling reaction using efficient catalysts in eco-friendly media. Green Chem. 2019, 21, 381–405. [Google Scholar] [CrossRef]
  5. Shi, Y.; Yang, G.; Shen, B.; Yang, Y.; Yan, L.; Yang, F.; Liu, J.; Liao, X.; Yu, P.; Bin, Z.; et al. Insight into Regioselective Control in Aerobic Oxidative C-H/C-H Coupling for C3-Arylation of Benzothiophenes: Toward Structurally Nontraditional OLED Materials. J. Am. Chem. Soc. 2021, 143, 21066–21076. [Google Scholar] [CrossRef]
  6. Dhangar, G.; Luis Serrano, J.; Schulzke, C.; Gunturu, K.C.; Kapdi, A.R. Palladacycle-Catalyzed Triple Suzuki Coupling Strategy for the Synthesis of Anthracene-Based OLED Emitters. ACS Omega 2017, 2, 3144–3156. [Google Scholar] [CrossRef]
  7. Guo, T.; Liang, J.J.; Yang, S.; Chen, H.; Fu, Y.N.; Han, S.L.; Zhao, Y.H. Palladium-catalyzed oxidative C-H/C-H cross-coupling of imidazopyridines with azoles. Org. Biomol. Chem. 2018, 16, 6039–6046. [Google Scholar] [CrossRef]
  8. Zhu, C.; Liu, J.; Li, M.-B.; Backvall, J.-E. Palladium-catalyzed oxidative dehydrogenative carbonylation reactions using carbon monoxide and mechanistic overviews. Chem. Soc. Rev. 2020, 49, 341–353. [Google Scholar] [CrossRef] [Green Version]
  9. Sun, N.; Wang, C.; Wang, H.; Yang, L.; Jin, P.; Zhang, W.; Jiang, J. Multifunctional Tubular Organic Cage-Supported Ultrafine Palladium Nanoparticles for Sequential Catalysis. Angew. Chem.—Int. Ed. 2019, 58, 18011–18016. [Google Scholar] [CrossRef]
  10. Zhou, E.; Jin, J.; Zheng, K.; Zhang, L.; Xu, H.; Shen, C. Novel Recyclable Pd/H-MOR Catalyst for Suzuki-Miyaura Coupling and Application in the Synthesis of Crizotinib. Catalysts 2021, 11, 1213. [Google Scholar] [CrossRef]
  11. Wei, Z.; Xie, Z.; Gao, L.; Wang, Y.; Sun, H.; Jian, Y.; Zhang, G.; Xu, L.; Yang, J.; Zhang, W.; et al. Highly Crystallized Pd/Cu Nanoparticles on Activated Carbon: An Efficient Heterogeneous Catalyst for Sonogashira Cross-Coupling Reaction. Catalysts 2020, 10, 192. [Google Scholar] [CrossRef] [Green Version]
  12. Peramo, A.; Abdellah, I.; Pecnard, S.; Mougin, J.; Martini, C.; Couvreur, P.; Huc, V.; Desmaele, D. A Self-Assembling NHC-Pd-Loaded Calixarene as a Potent Catalyst for the Suzuki-Miyaura Cross-Coupling Reaction in Water. Molecules 2020, 25, 1459. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  13. Tabasso, S.; Gaudino, E.C.; Acciardo, E.; Manzoli, M.; Giacomino, A.; Cravotto, G. Microwave-Assisted Dehydrogenative Cross Coupling Reactions in γ-valerolactone with a Reusable Pd/β-cyclodextrin Crosslinked Catalyst. Molecules 2019, 24, 288. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  14. Wang, S.-S.; Yang, G.-Y. Recent developments in low-cost TM-catalyzed Heck-type reactions (TM = transition metal, Ni, Co, Cu, and Fe). Catal. Sci. Technol. 2016, 6, 2862–2876. [Google Scholar] [CrossRef]
  15. Pourjavadi, A.; Kohestanian, M.; Keshavarzi, N. Immobilization of Au nanoparticles on poly(glycidyl methacrylate)-functionalized magnetic nanoparticles for enhanced catalytic application in the reduction of nitroarenes and Suzuki reaction. Appl. Organomet. Chem. 2020, 34, e5828. [Google Scholar] [CrossRef]
  16. Kataria, M.; Kumar, M.; Singh, Z.; Bhalla, V. Gold Nanoparticles Immobilized Polymeric PBI Derivative: Productive, Portable, and Photocatalytic System for Heck Coupling. ACS Sustain. Chem. Eng. 2018, 6, 8223–8229. [Google Scholar] [CrossRef]
  17. Al-shaikh, H.; Lasri, J.; Knight, J.G. Bimetallic Ru: Co Mesoporous Nanoparticles Stabilized by PEG and Imidazolium Ionic Liquid Based [KIT-6] as an Efficient Heterogeneous Catalyst for Suzuki–Miyaura Cross-Couplings in H2O:EtOH Solution. Catal. Lett. 2022. [Google Scholar] [CrossRef]
  18. Kim, S.; Varga, G.; Seo, M.; Sápi, A.; Rácz, V.; Gómez-Pérez, J.F.; Sebők, D.; Lee, J.; Kukovecz, Á.; Kónya, Z. Nesting Well-Defined Pt Nanoparticles within a Hierarchically Porous Polymer as a Heterogeneous Suzuki–Miyaura Catalyst. ACS Appl. Nano Mater. 2021, 4, 4070–4076. [Google Scholar] [CrossRef]
  19. Sharma, K.; Kumar, M.; Bhalla, V. Aggregates of the pentacenequinone derivative as reactors for the preparation of Ag@Cu2O core-shell NPs: An active photocatalyst for Suzuki and Suzuki type coupling reactions. Chem. Commun. (Camb.) 2015, 51, 12529–12532. [Google Scholar] [CrossRef] [PubMed]
  20. Danqing, L.; Ming, J.; Li, L.; Mohammadnia, M. Preparation and characterization of Cu supported on 2-(1H-benzo [d] imidazol-2-yl) aniline-functionalized Fe3O4 nanoparticles as a novel magnetic catalyst for Ullmann and Suzuki cross-coupling reactions. Appl. Organomet. Chem. 2020, 34, e5820. [Google Scholar] [CrossRef]
  21. Bankar, D.B.; Kanade, K.G.; Hawaldar, R.R.; Arbuj, S.S.; Shinde, M.D.; Takle, S.P.; Amalnerkar, D.P.; Shinde, S.T. Facile synthesis of nanostructured Ni-Co/ZnO material: An efficient and inexpensive catalyst for Heck reactions under ligand-free conditions. Arab. J. Chem. 2020, 13, 9005–9018. [Google Scholar] [CrossRef]
  22. Kiani, M.; Bagherzadeh, M.; Meghdadi, S.; Fadaei-Tirani, F.; Babaie, M.; Schenk-Joß, K. Promising new catalytic properties of a Co (II)-carboxamide complex and its derived Co3O4 nanoparticles for the Mizoroki-Heck and the Epoxidation reactions. Appl. Organomet. Chem. 2020, 34, e5911. [Google Scholar] [CrossRef]
  23. Adak, L.; Hatakeyama, T.; Nakamura, M. Iron-Catalyzed Cross-Coupling Reactions Tuned by BulkyOrtho-Phenylene Bisphosphine Ligands. Bull. Chem. Soc. Jpn. 2021, 94, 1125–1141. [Google Scholar] [CrossRef]
  24. Yamamoto, K.; Imaoka, T.; Tanabe, M.; Kambe, T. New Horizon of Nanoparticle and Cluster Catalysis with Dendrimers. Chem. Rev. 2020, 120, 1397–1437. [Google Scholar] [CrossRef] [PubMed]
  25. Li, Z.; Ji, S.F.; Liu, Y.W.; Cao, X.; Tian, S.B.; Chen, Y.J.; Niu, Z.G.; Li, Y.D. Well-Defined Materials for Heterogeneous Catalysis: From Nanoparticles to Isolated Single-Atom Sites. Chem. Rev. 2020, 120, 623–682. [Google Scholar] [CrossRef] [PubMed]
  26. Hulsey, M.J.; Lim, C.W.; Yan, N. Promoting heterogeneous catalysis beyond catalyst design. Chem. Sci. 2020, 11, 1456–1468. [Google Scholar] [CrossRef] [Green Version]
  27. Gao, Y.X.; Ding, Y. Nanoporous Metals for Heterogeneous Catalysis: Following the Success of Raney Nickel. Chem.—Eur. J. 2020, 26, 8845–8856. [Google Scholar] [CrossRef]
  28. Hui, Y.H.; Zhang, S.W.; Wang, W.T. Recent Progress in Catalytic Oxidative Transformations of Alcohols by Supported Gold Nanoparticles. Adv. Synth. Catal. 2019, 361, 2215–2235. [Google Scholar] [CrossRef]
  29. Narani, A.; Reddy Kannapu, H.P.; Natte, K.; Burri, D.R. Pd-Nanoparticles immobilized organo-functionalized SBA-15: An efficient heterogeneous catalyst for selective hydrogenation of C C double bonds of α,β-unsaturated carbonyl compounds. Mol. Catal. 2020, 497, 111200. [Google Scholar] [CrossRef]
  30. Hong, K.; Sajjadi, M.; Suh, J.M.; Zhang, K.; Nasrollahzadeh, M.; Jang, H.W.; Varma, R.S.; Shokouhimehr, M. Palladium Nanoparticles on Assorted Nanostructured Supports: Applications for Suzuki, Heck, and Sonogashira Cross-Coupling Reactions. ACS Appl. Nano Mater. 2020, 3, 2070–2103. [Google Scholar] [CrossRef]
  31. Koizumi, Y.; Jin, X.; Yatabe, T.; Miyazaki, R.; Hasegawa, J.Y.; Nozaki, K.; Mizuno, N.; Yamaguchi, K. Selective Synthesis of Primary Anilines from NH3 and Cyclohexanones by Utilizing Preferential Adsorption of Styrene on the Pd Nanoparticle Surface. Angew. Chem.—Int. Ed. 2019, 58, 10893–10897. [Google Scholar] [CrossRef] [PubMed]
  32. Kilic, A.; Gezer, E.; Durap, F.; Aydemir, M.; Baysal, A. Pd(II) supported dioxime functionalized Fe3O4 nanoparticles as efficient, eco-friendly and reusable catalysts for the Suzuki-Miyaura cross-coupling reaction in water. J. Organomet. Chem. 2019, 896, 129–138. [Google Scholar] [CrossRef]
  33. Liu, L.; Corma, A. Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles. Chem. Rev. 2018, 118, 4981–5079. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  34. Dong, Z.; Pan, H.; Gao, P.; Xiao, Y.; Fan, L.; Chen, J.; Wang, W. Palladium Immobilized on a Polyimide Covalent Organic Framework: An Efficient and Recyclable Heterogeneous Catalyst for the Suzuki–Miyaura Coupling Reaction and Nitroarene Reduction in Water. Catal. Lett. 2022, 152, 299–306. [Google Scholar] [CrossRef]
  35. Dong, Z.; Pan, H.; Chen, J.; Fan, L.; Guo, J.; Wang, W. Palladium Supported on Urea-Containing Porous Organic Polymers as Heterogeneous Catalysts for C-C Cross Coupling Reactions and Reduction of Nitroarenes. J. Saudi Chem. Soc. 2021, 25, 101317. [Google Scholar] [CrossRef]
  36. Gao, P.; Xiao, Y.; Dong, Z.; Pan, H.; Wang, W. Facile synthesis of palladium nanoparticles supported on urea-based porous organic polymers and its catalytic properties in Suzuki-Miyaura coupling. J. Saudi Chem. Soc. 2020, 24, 282–287. [Google Scholar] [CrossRef]
  37. Dong, Z.; Pan, H.; Yang, L.; Fan, L.; Xiao, Y.; Chen, J.; Wang, W. Porous organic polymer immobilized copper nanoparticles as heterogeneous catalyst for efficient benzylic C-H bond oxidation. J. Saudi Chem. Soc. 2022, 26, 101397. [Google Scholar] [CrossRef]
Molecules 27 04777 sch001 550
Scheme 1. Preparation of Pd@AEPOP.
Scheme 1. Preparation of Pd@AEPOP.
Molecules 27 04777 sch001
Molecules 27 04777 g001 550
Figure 1. CP-MAS 13C NMR spectra of AEPOP.
Figure 1. CP-MAS 13C NMR spectra of AEPOP.
Molecules 27 04777 g001
Molecules 27 04777 g002 550
Figure 2. SEM and TEM characterizations of AEPOP and Pd@AEPOP. (a) SEM image of AEPOP, (b–e) Pd NPs in different scales, (f) diffraction fringe of Pd.
Figure 2. SEM and TEM characterizations of AEPOP and Pd@AEPOP. (a) SEM image of AEPOP, (b–e) Pd NPs in different scales, (f) diffraction fringe of Pd.
Molecules 27 04777 g002
Molecules 27 04777 g003 550
Figure 3. PXRD patterns of AEPOP and Pd@AEPOP.
Figure 3. PXRD patterns of AEPOP and Pd@AEPOP.
Molecules 27 04777 g003
Molecules 27 04777 sch002 550
Scheme 2. The recyclability of Pd@AEPOP.
Scheme 2. The recyclability of Pd@AEPOP.
Molecules 27 04777 sch002
Molecules 27 04777 sch003 550
Scheme 3. Catalytic application extension of Pd@AEPOP.
Scheme 3. Catalytic application extension of Pd@AEPOP.
Molecules 27 04777 sch003
Table
Table 1. Identification of reaction conditions a.
Table 1. Identification of reaction conditions a.
Molecules 27 04777 i001
EntryBaseSolventTemp.Time (h)Yield b
1K2CO3DMSO905Trace
2K2CO3DMF90536
3K2CO3H2O90510
4K2CO3DMF90540
5Et3NDMF90555
6Cs2CO3DMF905Trace
7Et3NDMF100563
8Et3NDMF110571
9Et3NDMF120575
10Et3NDMF1201095
a Reaction conditions: 4-methyl iodobenzene 1 mmol, styrene 1.2 mmol, Pd@AEPOP (20 mg, 0.8 mol% Pd content), base 1.5 mmol, solvent 2 mL. b Isolated yield.
Table
Table 2. Substrate scopes of Heck reactions a.
Table 2. Substrate scopes of Heck reactions a.
Molecules 27 04777 i002
EntryArIRYield b
14-Me-PhPh95
2PhPh99
34-tBu-PhPh93
43-Cl-PhPh98
5PhCOOEt98
63-Cl-PhCOOEt99
74-Cl-PhCOOEt99
82-Me-PhCOOEt92
93-Me-PhCOOEt98
104-Me-PhCOOEt99
114-MeO-PhCOOEt99
a Aryl iodides (1 mmol), alkenes (1.2 mmol, 1.2 equiv.), Et3N (1.5 mmol, 1.5 equiv.), DMF (2 mL), Pd@AEPOP (20 mg, 0.8 mol% Pd content), 120 °C, 10 h. b Isolated yield.
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Shi, G.; Dong, Z. Palladium Supported on Porous Organic Polymer as Heterogeneous and Recyclable Catalyst for Cross Coupling Reaction. Molecules 2022, 27, 4777. https://doi.org/10.3390/molecules27154777

AMA Style

Shi G, Dong Z. Palladium Supported on Porous Organic Polymer as Heterogeneous and Recyclable Catalyst for Cross Coupling Reaction. Molecules. 2022; 27(15):4777. https://doi.org/10.3390/molecules27154777

Chicago/Turabian Style

Shi, Guanying, and Zhenhua Dong. 2022. "Palladium Supported on Porous Organic Polymer as Heterogeneous and Recyclable Catalyst for Cross Coupling Reaction" Molecules 27, no. 15: 4777. https://doi.org/10.3390/molecules27154777

Article Metrics

Back to TopTop