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Article

Copper Catalysts Anchored on Cysteine-Functionalized Polydopamine-Coated Magnetite Particles: A Versatile Platform for Enhanced Coupling Reactions

by
Yu-Jeong Jo
1,
Seung-Woo Park
1,
Ueon Sang Shin
2,3,* and
Seung-Hoi Kim
1,*
1
Department of Chemistry, Dankook University, Cheonan 31116, Republic of Korea
2
Department of Nanobiomedical Science, BK21 FOUR NBM Global Research Center for Regenerative Medicine, Dankook University, Cheonan 31116, Republic of Korea
3
Institute of Tissue Regeneration Engineering (ITREN), Dankook University, Cheonan 31116, Republic of Korea
*
Authors to whom correspondence should be addressed.
Molecules 2024, 29(21), 5121; https://doi.org/10.3390/molecules29215121
Submission received: 2 October 2024 / Revised: 23 October 2024 / Accepted: 25 October 2024 / Published: 30 October 2024
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Abstract

:
Cysteine plays a crucial role in the development of an efficient copper-catalyst system, where its thiol group serves as a strong anchoring site for metal coordination. By immobilizing copper onto cysteine-modified, polydopamine-coated magnetite particles, this advanced catalytic platform exhibits exceptional stability and catalytic activity. Chemical modification of the polydopamine (PDA) surface with cysteine enhances copper salt immobilization, leading to the formation of the Fe3O4@PDA-Cys@Cu platform. This system was evaluated in palladium-free, copper-catalyzed Sonogashira coupling reactions, effectively catalyzing the coupling of terminal acetylenes with aryl halides. Additionally, the Fe3O4@PDA-Cys@Cu platform was employed in click reactions, confirming the enhanced catalytic efficiency due to increased copper content. The reusability of the platform was further investigated, demonstrating improved performance, especially in recyclability tests in click reaction, making it a promising candidate for sustainable heterogeneous catalysis.

1. Introduction

Transition metal-catalyzed cross-coupling reactions have become increasingly prevalent in contemporary synthetic organic chemistry, facilitating the creation of vital carbon–carbon (C–C) bonds [1,2]. Within the spectrum of strategies for synthesizing biologically or industrially significant organic functional molecules, the Sonogashira coupling reaction emerges as a pivotal technique, notably facilitating the formation of carbon–carbon bonds, particularly in the synthesis of alkynes [3,4].
The coupling reaction between aromatic acetylenes and aryl halides was independently reported in 1975 by Cassar [5], Heck [6], and Sonogashira [7]. To perform those coupling reactions, a wide range of palladium catalysts, along with copper co-catalysts, have been frequently employed.
Although the reaction can be performed under mild conditions, applying the Sonogashira reaction to industrial or pharmaceutical synthesis became challenging due to the toxicity and air sensitivity of phosphine ligands, as well as the high price of palladium [8]. To overcome the shortcomings of the aforementioned reaction conditions, various approaches have focused on the development of more sustainable and cost-effective catalytic systems, such as palladium- and phosphine-free Sonogashira-type coupling reactions. In this context, copper has emerged as a promising candidate due to its earth abundance and low toxicity [9,10,11,12,13,14,15,16,17,18,19,20,21,22,23]. Along with copper metal, several transition metal complexes, including Fe [24,25,26], Zn [27], Co [28,29], Ag [30], Ni [31], Ru [32,33], and Au [34], have been efficiently utilized for the execution of Sonogashira coupling reactions.
Interestingly, recent scientific artworks have highlighted the growing interest in Pd-free copper-catalyzed Sonogashira coupling reactions, with the aim of overcoming the limitations associated with palladium-based catalysis [17,35,36]. More importantly, despite the impressive advancements in Csp–Csp2 bond construction utilizing various transition metal catalytic systems over the past few decades, the development of heterogeneous Cu-based catalyst systems remains an ongoing challenge. To date, several heterogeneous copper catalytic protocols, including appropriate rigid support, have been successfully developed and applied to Sonogashira coupling [36].
Of the aforementioned outcomes, utilizing the magnetic support attracted our attention [37,38,39]. In our previous study, we demonstrated the preparation and application of a heterogeneous copper catalytic platform, where copper was directly immobilized on the surface of polydopamine (PDA)-coated magnetite (Fe3O4@PDA@Cu) [40]. Although this platform demonstrated satisfactory performance as a heterogeneous copper catalyst in click reactions, we envisioned a higher copper content in this type of magnetite-based platform. To achieve this goal, we designed further modifications to the PDA surface of magnetite by introducing a biocompatible substance. Cysteine was chosen as the optimal compound for this decoration.
According to previous studies, cysteine, which contains amine, carboxy, and thiol groups, has been widely utilized for effective anchoring with PDA by covalently linking to PDA-modified core–shell nanoparticles for secondary modification [41,42,43]. As a result, the cysteine-modified PDA-magnetite particles played a significant role in removing Pb from wastewater [44]. Interestingly, a recent study demonstrated an example of cysteine-modified layered double hydroxides (LDHs)-coated magnetite nanoparticles for copper anchoring and its application in click reactions [45]. These outcomes strongly supported our anticipation of enhancing copper immobilization through the action of cysteine moiety on the surface of the Fe3O4@PDA-Cys platform.
Building on the concepts above, we developed a novel magnetically recoverable copper catalytic platform using cysteine as a biocompatible substrate (denoted as Fe3O4@PDA-Cys@Cu). Cysteine’s functional groups enhance copper-metal immobilization, making this platform highly effective in Pd-free Cu-catalyzed Sonogashira coupling reactions. Additionally, increased copper content was shown to enhance catalytic recyclability, as demonstrated in a comparative study of click reactions. This versatile platform offers promising potential for a range of organic coupling reactions.

2. Results

2.1. Characterization

Characterization of the obtained platform was performed using several techniques, including FT-IR, TGA, EDX, and SEM. According to the ICP-OES analysis, the cysteine-modified magnetite particles (Fe3O4@PDA-Cys@Cu) contained a higher copper content (18.96%) compared to the unmodified platform (Fe3O4@PDA@Cu), which had 5.02%.
The thermal stability of the Fe3O4@PDA-Cys@Cu platform and related complexes was investigated using TGA (Figure 1). The negligible weight loss below 150 °C is attributed to the physically adsorbed volatile substances. Upon comparing the TGA analysis results, the difference between the Fe3O4@PDA@Cu and the cysteine-modified platform (Fe3O4@PDA-Cys@Cu) becomes even more pronounced. Interestingly, a very similar pattern was observed in the cysteine-modified platforms (Fe3O4@PDA-Cys and Fe3O4@PDA-Cys@Cu).
When examining the weight changes in the Fe3O4@PDA-Cys platform, the weight loss of cysteine occurred rapidly, whereas PDA showed a gradual weight loss attributed to the polymerized form of dopamine. A very similar two-stage weight loss was observed in the thermogram for the Fe3O4@PDA-Cys@Cu platform, which was prepared using the Fe3O4@PDA-Cys platform. These weight losses indicate the presence of PDA and cysteine grafted to the Fe3O4 surface. Based on the Fe3O4@PDA-Cys platform, a brief calculation of the composition ratio of each component showed that Fe3O4, PDA, and cysteine were present in a mole ratio of approximately 1:2:2.
Furthermore, a morphological feature of the Fe3O4@PDA-Cys@Cu was investigated using SEM–EDX and is provided in Figure 2. The EDX analyses of each platform clearly showed an increase in copper content in the Fe3O4@PDA-Cys platform compared to the Fe3O4@PDA platform.

2.2. Application to Organic Reactions

To verify the catalytic activity of the prepared Fe3O4@PDA-Cys@Cu platform, it was initially employed in the Sonogashira coupling reaction, a cross-coupling reaction involving aryl acetylenes and aryl halides.
Before the general application of the Fe3O4@PDA-Cys@Cu platform, we conducted a preliminary search for optimal parameters for the Sonogashira coupling reactions using phenyl acetylene (1a) and 4-iodoanisole (2a) as standard substrates (Table 1).
At first, the model reaction was carried out using excess equivalent (1.2 eq) of phenyl acetylene (1a) with 60 mg of Fe3O4@PDA-Cys@Cu platform in DMSO at 100 °C, affording the desired coupling product (3a) in 84% isolated yield (Table 1, Entry 1). Significantly, a remarkable improvement in isolated yield (up to 99%) was achieved by increasing the amount of the catalytic platform (up to 80 mg) employed under the same conditions (Table 1, Entry 2). Subsequent trials were conducted to identify a more versatile solvent system, which demonstrated the high efficiency of both ethanol and water as reaction media. For practical convenience, we chose to employ EtOH as the reaction solvent for further investigation. Decreasing the amount of the platform to 60 mg did not significantly affect the isolated yield (Table 1, Entries 5 and 6). Further attempts with 50 mg of Fe3O4@PDA-Cys@Cu platform demonstrated relatively lower catalytic efficiency under similar conditions (Table 1, Entry 7). The use of equimolar amounts of 1a and 2a resulted in a slightly disappointing outcome (Table 1, Entry 8). Interestingly, reaction temperature turned out to be a critical factor for the successful completion of the reaction (Table 1, Entry 9).
With the optimization tests, the scope and applicability of the novel catalytic platform were further explored using various substrates (Table 2). Firstly, the investigation was conducted using 1a and aryl halides containing a C–I bond in the presence of Fe3O4@PDA-Cys@Cu platform under standard conditions. Initially, 2-iodotoluene (2b) was reacted with 1a, resulting in the formation of 1-methyl-2-(phenylethynyl)benzene (3b) with an isolated yield of 91% (Table 2, Entry 1). Additionally, the reaction of 1a with 3-fluoro-iodobenzene proceeded well, yielding the corresponding coupled product (3c) in excellent isolated yields (Table 2, Entry 2). In contrast to these positive outcomes, relatively lower performance was observed in the coupling reactions with 4-chloroiodobenzene (2d) and 3-cyano-iodobenzene (2e). Interestingly, a polar functional group (OH) on aryl iodide (2f) was well tolerated, yielding the desired product (3f) in excellent yield (Table 2, Entry 5).
The substrate scope of acetylene was also investigated using various aryl acetylenes (1b–1f) under standard conditions. Overall, the reaction outcomes were consistent with those observed for 1a, confirming the catalytic efficiency of the developed reaction platform. Entries 6 and 7 in Table 2 demonstrate that 3-iodoaniline (2g) and 3-fluoro-iodobenzene (2c) were effective substrates for the synthesis of their respective asymmetric acetylene derivatives (3g and 3h) from 1-ethynyl-4-methylbenzene (1b) using the optimized Sonogashira coupling (Table 2, Entries 6 and 7). Similar catalytic performance was observed when various aryl acetylenes, such as 4-ethynylbenzonitrile (1c) and 1-ethynyl-4-methoxybenzene (1d), were used. The corresponding products (3i and 3j, respectively) were effectively obtained with excellent yields (Table 2, Entries 8 and 9). Furthermore, the presence of bromine (1e) and hydroxyl (1f) groups on the aryl acetylene rings did not affect the reaction outcome (Table 2, Entries 10 and 11). The reaction conditions used in this study were well tolerated to provide the final coupling products (3k and 3l) in an excellent manner.
To further extend the scope of this green protocol, we studied the coupling of 1a with various aryl halides bearing a C–Br bond, including 4-bromobenzonitrile, 2-bromothiophene, and 2-bromopyridine. Unfortunately, the reactions proceeded sluggishly or resulted in inseparable mixtures (Table 2, Entries 12–14).
Next, the recyclability of the novel catalytic platform was explored to ensure its advantage as a heterogeneous catalytic system (Table 3). Following standard procedures, a recycling test was carried out using 1a and 2a. After each cycle, the catalyst was effortlessly retrieved using an external magnet, washed consecutively with fresh water and acetone, and subsequently dried in air. The results from the recycling test indicate that the present platform demonstrates high potential as a recoverable and reusable heterogeneous catalytic system for Sonogashira coupling under mild conditions.
As mentioned before, we previously disclosed a novel heterogeneous copper catalyst immobilized on polydopamine-coated magnetite for click reaction [40]. In our previous study, the catalyst was prepared by immobilizing Cu(OAc)2 salt onto polydopamine-coated magnetite (denoted as Fe3O4@PDA@Cu). The catalytic activity of the resulting Fe3O4@PDA@Cu platform was investigated in a click reaction, utilizing three-component reactions of azide, alkyne, and benzyl surrogates in water, which provided the corresponding 1,2,3-triazoles in high yields. Despite the positive outcomes using the Fe3O4@PDA@Cu platform, unsatisfactory results were observed in recycling tests (see Table 5).
Despite numerous approaches utilizing magnetite-based copper catalytic systems for click reaction [40], there remains a need for versatile routes that focus on catalyst recyclability and reusability. Here, to expand the library of click reactions catalyzed by magnetic nanoparticle-supported copper catalysts and conduct a comparative study, we further carried out click reactions using various substrates in the presence of our newly designed Fe3O4@PDA-Cys@Cu platform. For a simple comparison, the results were disclosed in parallel with those obtained using our previous Fe3O4@PDA@Cu platform, as shown in Table 4.
In general, no significant differences were observed in the overall reactivity when using Fe3O4@PDA@Cu and Fe3O4@PDA-Cys@Cu as catalysts in the click reaction, respectively. In both cases, cyclization proceeded smoothly, providing 1,4-disubstituted-1,2,3-triazoles in excellent yields regardless of the functionality of acetylenes or benzyl halides. As evidenced by the yield of the target product, each catalyst system exhibited highly effective catalytic activity in the click reaction.
Next, the recyclability of the novel catalytic platform in click reaction was explored to ensure its advantage over our previous non-modified Fe3O4@PDA@Cu platform [41]. Following standard procedures, two different platforms—non-cysteine-modified (Fe3O4@PDA@Cu) and cysteine-modified (Fe3O4@PDA-Cys@Cu)—were employed in a recycling test (Table 5). The coupling of phenyl acetylene (1a), benzyl bromide, and sodium azide was selected for the recycling test, and the efficiency of each platform was verified by comparing the isolated yields of the coupling product (4a), which are comparatively displayed. As shown in Table 5, the catalytic activity of Fe3O4@PDA@Cu and Fe3O4@PDA-Cys@Cu in recycling tests for the click reaction demonstrated significant differences, clearly indicating the superior effectiveness of the Fe3O4@PDA-Cys@Cu catalyst. In contrast, the Fe3O4@PDA@Cu catalyst, as used in our previous study, showed a much more limited catalytic recycling ability, further highlighting the improved performance of the cysteine-modified platform in these reactions.
We hypothesized that these differences could be attributed to the variation in copper content retained within the recycled platforms after use. To verify our assumption, we performed an ICP analysis to quantify the decrease in copper content before and after use. In our previous study with Fe3O4@PDA@Cu, the copper content dropped from 5.01% to 0.04%. Interestingly, in the current study using Fe3O4@PDA-Cys@Cu, the reduction in copper content was notably less, decreasing from 18.96% to 17.41% after seven recycling cycles.
Furthermore, a similarly modest reduction in copper content was also observed during the Sonogashira coupling reaction using Fe3O4@PDA-Cys@Cu and confirmed by EDX analysis (Figure 3).

3. Conclusions

We developed and thoroughly characterized a novel, recoverable catalytic platform composed of magnetic particles (Fe3O4), copper salts, polydopamine, and cysteine (Fe3O4@PDA-Cys@Cu). Using a range of spectroscopic methods, including FT-IR, EDX, TGA, SEM, and ICP-OES, we confirmed the enriched copper content in this platform. The enhanced immobilization of copper salt is attributed to the cysteine modification of the PDA surface on the magnetite.
In application, the increased copper content proved highly effective in organic reactions. For example, the Fe3O4@PDA-Cys@Cu platform successfully facilitated the Sonogashira coupling reaction, yielding the desired Csp–Csp2 coupling products under mild conditions. Various types of aryl acetylenes and aryl iodides were suitable for the coupling reaction, although aryl halides with carbon–bromine bonds showed limitations. Furthermore, the increased copper content in the platform enhanced its catalytic efficiency in click reactions, particularly in recycling tests. A three-component reaction involving terminal alkynes, benzyl surrogates, and sodium azide in an aqueous environment yielded 1,4-disubstituted-1,2,3-triazoles in good to excellent isolated yields. Notably, the recycling test highlighted the clear advantage of cysteine modification in the PDA-coated magnetite-based nanoparticle platform. Compared to our previous study [40], the reusability of the platform was significantly improved up to the seventh recycling run.
In conclusion, the biocompatible material cysteine played a key role in enhancing copper immobilization during the preparation of a magnetically recoverable catalytic platform. This modified copper-based platform exhibited significantly enhanced catalytic activity in both Sonogashira coupling and click reactions.

4. Materials and Methods

4.1. Procedure for Fe3O4@PDA

Fe3O4 nanoparticles were prepared using the co-precipitation method, following the literature [46,47]. An iron salt solution was obtained by mixing FeCl3·6H2O (34.6 g) and FeCl2·4H2O (12.7 g), in the molar ratio of 2:1, in 1.5 L of deionized water under nitrogen at room temperature. By dropwise addition of NH3 solution, the pH was adjusted to 12. A black precipitate was formed after continuously stirring for 1 h. The precipitate was magnetically separated and washed four times with deionized water until the solution reached a pH of 8, followed by washing with ethanol (30 mL × 2). Then, the resulting precipitate was dried under vacuum at 50 °C overnight.
Next, for the PDA-coating of magnetite, a mixture of Fe3O4 MNPs (5.0 g) and tris buffer (1.0 M, pH 8.5, 50 mL) was sonicated for 30 min. Subsequently, dopamine hydrochloride (10.0 g) was added to the mixed solution, and the mixture was stirred at room temperature for 24 h. Then, the resulting black particles (Fe3O4@PDA) were collected using a magnet and washed with H2O (30 mL × 3) and ethanol (30 mL × 2). The obtained platform was dried in vacuum at 50 °C for 12 h.

4.2. Procedure for Fe3O4@PDA-Cys

A solution of Fe3O4@PDA particles (3.0 g) in H2O (200 mL) was sonicated for 3 h at room temperature. In a separate flask, L-cysteine (4.5 g) in H2O (100 mL) was sonicated for 1 h at room temperature. Next, the cysteine solution was then added to the Fe3O4@PDA solution, and the resulting mixture was stirred at 50 °C for 24 h. The black precipitates were filtered, washed sequentially with H2O (30 mL × 3) and EtOH (30 mL × 3), and then dried under vacuum at 50 °C for 24 h, providing 5.0 g of the Fe3O4@PDA-Cys platform.

4.3. Procedure for Fe3O4@PDA-Cys@Cu

A solution of Fe3O4@PDA-Cys particles (1.4 g) in EtOH/H2O (1:1, v/v, 80 mL) was sonicated for 1 h at room temperature. In a separated flask, copper acetate (1.4 g) was added and then sonicated for 30 min. Next, the two solutions were then combined, and the resulting mixture was stirred at room temperature for 24 h. The obtained particles were collected using a magnet and washed with water (20 mL × 3) and ethanol (20 mL × 3). After drying under vacuum at 50 °C for 12 h, 1.1 g of Fe3O4@PDA-Cys@Cu was obtained.

4.4. General Procedure for Sonogashira Coupling

To a round-bottom flask equipped with a magnetic bar, phenyl acetylene (1a, 0.36 g, 3.6 mmol), 4-iodoanisole (2a, 0.7 g, 3.0 mmol), Fe3O4@PDA-Cys@Cu (60 mg), and EtOH (4.0 mL) were added. Then, the mixture was stirred at a refluxing temperature. After completion, the reaction mixture was cooled down to room temperature. The mixture was filtered, and the filtrate was acidified with 3 M HCl aqueous solution. The aqueous layer was extracted with diethyl ether (3 × 10 mL). The combined organic layers were washed with brine, dried with anhydrous Na2SO4, and evaporated under reduced pressure. The crude mixture was purified by column chromatography on silica gel using hexanes only, yielding 0.61 g of 1-methoxy-4-(phenylethynyl)benzene (3a) as a white solid; m.p. 92–93 °C. 1H NMR (400 MHz, DMSO-d6) δ (ppm): 7.49–7.94 (m, 4H), 7.43–7.39 (m, 3H), 7.00–6.98 (dd, J = 6.8, 2.0 Hz, 2H), and 3.80 (s, 3H). 13C NMR (100 MHz, DMSO-d6) δ (ppm): 160.0, 133.4, 131.6, 129.2, 128.9, 123.1, 114.9, 114.7, 89.9, 88.4, and 55.7.

4.5. General Procedure for Click Reaction

The mixture of benzyl bromide (0.51 mg, 3.0 mmol), phenyl acetylene (0.37 mg, 3.6 mmol), and sodium azide (0.23 mg, 3.6 mmol) was stirred at 90 °C in the presence of Fe3O4@PDA-Cys@Cu platform (70 mg) in H2O. After being refluxed for 5.0 h, the mixture was decanted with the aid of an external magnet. The aqueous layer was then extracted with ethyl acetate (3 × 10 mL). The combined organic layers were washed with brine, dried with anhydrous Na2SO4, and evaporated under reduced pressure. The crude mixture was purified by column chromatography on silica gel [hexanes (90%)/ethyl acetate (10%)], yielding 0.69 g of 1-benzyl-4-phenyl-1H-1,2,3-triazole (4a) as a white solid; m.p. 127–128 °C. 1H NMR (400 MHz, CDCl3) δ (ppm): 7.69–7.66 (m, 2H), 7.56 (s, 1H), 7.29–7.22 (m, 5H), 7.21–7.16 (m, 3H), and 5.41 (s, 2H). 13C NMR (100 MHz, CDCl3) δ (ppm): 148.2, 134.8, 130.6, 129.1, 128.8, 128.7, 128.2, 128.0, 125.7, 119.7, and 54.1.

Supplementary Materials

The following supporting information can be downloaded at https://www.mdpi.com/article/10.3390/molecules29215121/s1, 1H and 13C NMR data and copies of spectra. Reference [48] is cited in the supplementary materials.

Author Contributions

Synthesis and characterization, Y.-J.J. and S.-W.P.; writing—original draft preparation, S.-H.K.; writing—review and editing, S.-H.K. and U.S.S. 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

Data are contained within the article and Supplementary Materials.

Conflicts of Interest

The authors declare no conflicts of interest.

References

  1. Johansson Seechurn, C.C.C.; Kitching, M.O.; Colacot, T.J.; Snieckus, V. Palladium-Catalyzed Cross-Coupling: A Historical Contextual Perspective to the 2010 Nobel Prize. Angew. Chem. Int. Ed. 2012, 51, 5062–5085. [Google Scholar] [CrossRef] [PubMed]
  2. Diederich, F. Metal-Catalyzed Cross-Coupling Reactions; Wiley-VCH: New York, NY, USA, 1997. [Google Scholar]
  3. Akhtar, R.; Zahoor, A.F.; Parveen, B.; Suleman, M. Development of environmental friendly synthetic strategies for Sonogashira cross coupling reaction: An update. Synth. Commun. 2019, 4, 167–192. [Google Scholar] [CrossRef]
  4. Chinchilla, R.; Nájera, C. Recent advances in Sonogashira reactions. Chem. Soc. Rev. 2011, 40, 5084–5121. [Google Scholar] [CrossRef] [PubMed]
  5. Cassar, L. Synthesis of aryl- and vinyl-substituted acetylene derivatives by the use of nickel and palladium complexes. J. Organomet. Chem. 1975, 93, 253–257. [Google Scholar] [CrossRef]
  6. Dieck, H.A.; Heck, R.F. Palladium catalyzed synthesis of aryl, heterocyclic and vinylic acetylene derivatives. J. Organomet. Chem. 1975, 93, 259–263. [Google Scholar] [CrossRef]
  7. Sonogashira, K.; Tohda, Y.; Hagihara, N. A convenient synthesis of acetylenes: Catalytic substitutions of acetylenic hydrogen with bromoalkenes, iodoarenes and bromopyridines. Tetrahedron Lett. 1975, 16, 4467–4470. [Google Scholar] [CrossRef]
  8. Heuze, K.; Mery, D.; Gauss, D.; Astruc, D. Copper-free, recoverable dendritic Pd catalysts for the Sonogashira reaction. Chem. Commun. 2003, 2274–2275. [Google Scholar] [CrossRef]
  9. Thathagar, M.B.; Beckers, J.; Rothenberg, G. Palladium-free and ligand-free Sonogashira cross-coupling. Green Chem. 2004, 6, 215–218. [Google Scholar] [CrossRef]
  10. Ghabdian, M.; Nasseri, M.A.; Allahresani, A.; Motavallizadehkakhky, A. Heterogenized Cu (II) salen complex grafted on graphene oxide nanosheets as a precursing catalyst for the Pd-free Sonogashira coupling. Appl. Organomet. Chem. 2018, 32, e4545. [Google Scholar] [CrossRef]
  11. Ma, D.; Liu, F. CuI-catalyzed coupling reaction of aryl halides with terminal alkynes in the absence of palladium and phosphine. Chem. Commun. 2004, 1934–1935. [Google Scholar] [CrossRef]
  12. Lina, C.X.; Zhua, J.F.; Lia, Q.S.; Aoa, L.H.; Jina, Y.J.; Xua, F.B.; Hua, F.Z.; Yuana, Y.F. 2,5-Bis(2-(diphenylphosphino)phenyl)-1,3,4-oxadiazole ligands and their Cu(I) complexes for Sonogashira coupling reaction. Appl. Organomet. Chem. 2014, 28, 298–303. [Google Scholar] [CrossRef]
  13. Okuro, K.; Furuune, M.; Enna, M.; Miura, M.; Nomura, M. Synthesis of aryl- and vinylacetylene derivatives by copper-catalyzed reaction of aryl and vinyl iodides with terminal alkynes. J. Org. Chem. 1993, 58, 4716–4721. [Google Scholar] [CrossRef]
  14. Saejueng, P.; Bates, C.G.; Venkataraman, D. Copper(I)-Catalyzed Coupling of Terminal Acetylenes with Aryl or Vinyl Halides. Synthesis 2005, 10, 1706–1712. [Google Scholar] [CrossRef]
  15. Gujadhur, R.K.; Bates, C.G.; Venkataraman, D. Formation of Aryl−Nitrogen, Aryl−Oxygen, and Aryl−Carbon Bonds Using Well-Defined Copper(I)-Based Catalysts. Org. Lett. 2001, 3, 4315–4317. [Google Scholar] [CrossRef]
  16. Li, J.H.; Li, J.L.; Wang, D.P.; Pi, S.F.; Xie, Y.X.; Zhang, M.B.; Hu, X.C. CuI-Catalyzed Suzuki−Miyaura and Sonogashira Cross-Coupling Reactions Using DABCO as Ligand. J. Org. Chem. 2007, 72, 2053–2057. [Google Scholar] [CrossRef]
  17. Thomas, A.M.; Sujatha, A.; Anilkumar, G. Recent advances and perspectives in copper-catalyzed Sonogashira coupling reactions. RSC Adv. 2014, 4, 21688–21698. [Google Scholar] [CrossRef]
  18. Petrignet, J.; Ngi, S.I.; Abarbri, M.; Thibonnet, J. Short and convenient synthesis of two natural phthalides by a copper(I) catalysed Sonogashira/oxacyclisation copper(I) process. Tetrahedron Lett. 2014, 55, 982–984. [Google Scholar] [CrossRef]
  19. Hajipour, A.R.; Mohammadsaleh, F. Sonogashira reactions catalyzed by a new and efficient copper(I) catalyst incorporating N-benzyl DABCO chloride. Tetrahedron Lett. 2014, 55, 3459–3462. [Google Scholar] [CrossRef]
  20. Kodicherla, B.; Perumgani, C.P.; Mandapati, M.R. A reusable polystyrene-supported copper(II) catalytic system for N-arylation of indoles and Sonogashira coupling reactions in water. Appl. Catal. A Gen. 2014, 483, 110–115. [Google Scholar] [CrossRef]
  21. Zhao, H.; Huang, B.; Wu, Y.; Cai, M. MCM-41-immobilized Schiff base-pyridine bidentate copper(I) complex as a highly efficient and recyclable catalyst for the Sonogashira reaction. J. Organomet. Chem. 2015, 797, 21–28. [Google Scholar] [CrossRef]
  22. Monnier, F.; Taillefer, M. Catalytic C–C, C–N, and C–O Ullmann-Type Coupling Reactions. Angew. Chem. Int. Ed. 2009, 49, 6954–6971. [Google Scholar] [CrossRef] [PubMed]
  23. Wang, Z.; Wang, X.; Sun, H.; Zhu, Z.; Zhang, G.; Zhang, W.; Gao, Z. Triazine-Triazole Conjugates as Potent Ligands for Cu–Catalyzed Sonogashira Reaction. ChemistrySelect 2016, 3, 391–395. [Google Scholar] [CrossRef]
  24. Carril, M.; Correa, A.; Bolm, C. Iron-Catalyzed Sonogashira Reactions. Angew. Chem. Int. Ed. 2008, 47, 4862–4865. [Google Scholar] [CrossRef] [PubMed]
  25. Sindhu, K.S.; Thankachan, A.P.; Thomas, A.M.; Anilkumar, G. Iron-Catalyzed Sonogashira Type Cross-Coupling Reaction of Aryl Iodides with Terminal Alkynes in Water under Aerobic Conditions. ChemistrySelect 2016, 3, 556–559. [Google Scholar] [CrossRef]
  26. Volla, C.M.R.; Vogel, P. Iron/copper-catalyzed C–C cross-coupling of aryl iodides with terminal alkynes. Tetrahedron Lett. 2008, 49, 5961–5964. [Google Scholar] [CrossRef]
  27. Thankachan, A.P.; Sindhu, K.; Krishnan, K.K.; Anilkumar, G. An efficient zinc-catalyzed cross-coupling reaction of aryl iodides with terminal aromatic alkynes. Tetrahedron Lett. 2015, 56, 5525–5528. [Google Scholar] [CrossRef]
  28. Feng, L.; Liu, F.; Sun, P.; Bao, J. Sonogashira reaction of aryl halides with terminal alkynes catalyzed by cobalt hollow nanospheres. Synlett 2008, 9, 1415–1417. [Google Scholar] [CrossRef]
  29. Amrutha, S.; Radhika, S.; Anilkumar, G. Recent developments and trends in the iron- and cobalt-catalyzed Sonogashira reactions. Beilstein J. Org. Chem. 2022, 18, 262–285. [Google Scholar] [CrossRef]
  30. Fang, G.; Bi, X. Silver-catalysed reactions of alkynes: Recent advances. Chem. Soc. Rev. 2015, 44, 8124–8173. [Google Scholar] [CrossRef]
  31. Wang, Z.; Li, L.; Huang, Y. A general synthesis of ynones from aldehydes via oxidative C–C bond cleavage under aerobic conditions. J. Am. Chem. Soc. 2014, 136, 12233–12236. [Google Scholar] [CrossRef]
  32. Park, S.; Kim, M.; Koo, D.H.; Chang, S. Use of ruthenium/alumina as a convenient catalyst for copper-free sonogashira coupling reactions. Adv. Synth. Catal. 2004, 346, 1638–1640. [Google Scholar] [CrossRef]
  33. Garbacia, S.; Touzani, R.; Lavastre, O. Image analysis as a quantitative screening test in combinatorial catalysis: Discovery of an unexpected ruthenium-based catalyst for the Sonogashira reaction. J. Comb. Chem. 2004, 6, 297–300. [Google Scholar] [CrossRef] [PubMed]
  34. Corma, A.; Juárez, R.; Boronat, M.; Sánchez, F.; Iglesias, M.; García, H. Gold catalyzes the Sonogashira coupling reaction without the requirement of palladium impurities. Chem. Commun. 2001, 47, 1446–1448. [Google Scholar] [CrossRef]
  35. Arundhathi, K.; Vaishnavi, P.; Aneeja, T.; Anilkumar, G. Copper-catalyzed Sonogashira reactions: Advances and perspectives since 2014. RSC Adv. 2023, 13, 4823–4834. [Google Scholar] [CrossRef]
  36. Mohjer, F.; Mofatehnia, P.; Rangraz, Y.; Heravi, M.M. Pd-free, Sonogashira cross-coupling reaction. An update. J. Organomet. Chem. 2021, 936, 121712. [Google Scholar] [CrossRef]
  37. Nasseri, M.A.; Rezazadeh, Z.; Kazemnejadi, M.; Allahresani, A. Magnetic Cu–Schiff base complex with an ionic tail as a recyclable bifunctional catalyst for base/Pd-free Sonogashira coupling reaction. J. Iran. Chem. Soc. 2019, 16, 2693–2705. [Google Scholar] [CrossRef]
  38. Hajipour, A.R.; Rezaei, F.; Khorsandi, Z. Pd/Cu-free Heck and Sonogashira cross–coupling reaction by Co nanoparticles immobilized on magnetic chitosan as reusable catalyst. Green Chem. 2017, 19, 1353–1361. [Google Scholar] [CrossRef]
  39. Nasseri, M.A.; Rezazadeh, Z.; Kazemnejadi, M.; Allahresani, A. A Co–Cu bimetallic magnetic nanocatalyst with synergistic and bifunctional performance for the base-free Suzuki, Sonogashira, and C–N cross-coupling reactions in water. Dalton Trans. 2020, 49, 10645–10660. [Google Scholar] [CrossRef] [PubMed]
  40. Kwak, S.J.; Oh, S.S.; Ahn, Y.H.; Kim, S.H. A Novel Heterogeneous Copper Catalyst Immobilized on Polydopamine-Coated Magnetite for Click Reaction. ChemistrySelect 2023, 8, e20232515. [Google Scholar] [CrossRef]
  41. Shevate, R.; Kumar, M.; Karunakaran, M.; Hedhili, M.; Peinemann, K.V. Polydopamine/cysteine surface modified isoporous membranes with self-cleaning properties. J. Membr. Sci. 2017, 529, 185–194. [Google Scholar] [CrossRef]
  42. Zhao, Y.; Yeh, Y.W.; Liu, R.; You, J.M.; Qu, F.L. Facile deposition of gold nanoparticles on core-shell Fe3O4@polydopamine as recyclable nanocatalyst. Solid State Sci. 2015, 45, 9–14. [Google Scholar] [CrossRef]
  43. Ma, P.; Dai, C.; Jiang, S. Thioetherimide-modified cyanate ester resin with better molding performance for glass fiber reinforced composites. Polymers 2019, 11, 1458. [Google Scholar] [CrossRef]
  44. Yang, W.; Wang, Y.; Wang, Q.; Wu, J.; Duan, D.; Xu, Q.; Jian, S. Magnetically separable and recyclable Fe3O4@PDA covalent grafted by L-cysteine core-shell nanoparticles toward efficient removal of Pb2+. Vacuum 2021, 189, 110229. [Google Scholar] [CrossRef]
  45. Pazoki, F.; Salamatmanesh, A.; Bagheri, S.; Heydari, A. Synthesis and Characterization of Copper(I)-Cysteine Complex Supported on Magnetic Layered Double Hydroxide as an Efficient and Recyclable Catalyst System for Click Chemistry Using Choline Azide as Reagent and Reaction Medium. Catal. Lett. 2020, 150, 1186–1195. [Google Scholar] [CrossRef]
  46. Veisi, H.; Hemmati, S.; Safarimehr, P. In situ immobilized palladium nanoparticles on surface of poly-methyldopa coated-magnetic nanoparticles (Fe3O4@PMDA/Pd): A magnetically recyclable nanocatalyst for cyanation of aryl halides with K4[Fe(CN)6]. J. Catal. 2018, 365, 204–212. [Google Scholar] [CrossRef]
  47. Wu, J.; Ko, S.P.; Liu, H.; Kim, S.; Ju, J.; Kim, Y.K. Sub 5 nm magnetite nanoparticles: Synthesis, microstructure, and magnetic properties. Mater. Lett. 2007, 61, 3124–3129. [Google Scholar] [CrossRef]
  48. Hemmati, S.; Zangeneh, M.M.; Zangeneh, A. CuCl2 anchored on polydopamine coated-magnetic nanoparticles (Fe3O4@PDA/Cu(II)): Preparation, characterization and evaluation of its cytotoxicity, antioxidant, antibacterial, and antifungal properties. Polyhedron 2020, 177, 114327. [Google Scholar]
Molecules 29 05121 g001
Figure 1. Comparing TGA analyses of Fe3O4@PDA-Cys@Cu platform and related substrates.
Figure 1. Comparing TGA analyses of Fe3O4@PDA-Cys@Cu platform and related substrates.
Molecules 29 05121 g001
Molecules 29 05121 g002
Figure 2. EDX analyses of Fe3O4@PDA@Cu (up) and Fe3O4@PDA-Cys@Cu (down).
Figure 2. EDX analyses of Fe3O4@PDA@Cu (up) and Fe3O4@PDA-Cys@Cu (down).
Molecules 29 05121 g002
Molecules 29 05121 g003
Figure 3. EDX analysis of recovered Fe3O4@PDA-Cys@Cu.
Figure 3. EDX analysis of recovered Fe3O4@PDA-Cys@Cu.
Molecules 29 05121 g003
Table 1. Screening optimal parameters for the Sonogashira coupling.
Table 1. Screening optimal parameters for the Sonogashira coupling.
Molecules 29 05121 i001
Entry1a2aCu-PlatformSolventTemp.TimeYield a
13.6 mmol3.0 mmol60 mgDMSO100 °C4 h84%
23.6 mmol3.0 mmol80 mgDMSO100 °C4 h99%
33.6 mmol3.0 mmol80 mgEtOHreflux5 h99%
43.6 mmol3.0 mmol80 mgH2Oreflux5 h99%
53.6 mmol3.0 mmol70 mgEtOHreflux5 h99%
63.6 mmol3.0 mmol60 mgEtOHreflux5 h97%
73.6 mmol3.0 mmol50 mgEtOHreflux5 h93%
83.0 mmol3.0 mmol80 mgEtOHreflux4 h87%
93.6 mmol3.0 mmol70 mgEtOHrt24 htrace
a Isolated yield of 3a based on 2a.
Table 2. Sonogashira coupling.
Table 2. Sonogashira coupling.
Molecules 29 05121 i002
EntryAr1Ar2ProductYield a
1Molecules 29 05121 i003
(1a)		Molecules 29 05121 i004
(2b)		Molecules 29 05121 i005
(3b)		91%
2(1a)Molecules 29 05121 i006
(2c)		Molecules 29 05121 i007
(3c)		93%
3(1a)Molecules 29 05121 i008
(2d)		Molecules 29 05121 i009
(3d)		86%
4(1a)Molecules 29 05121 i010
(2e)		Molecules 29 05121 i011
(3e)		88%
5(1a)Molecules 29 05121 i012
(2f)		Molecules 29 05121 i013
(3f)		98%
6Molecules 29 05121 i014
(1b)		Molecules 29 05121 i015
(2g)		Molecules 29 05121 i016
(3g)		98%
7(1b)(2c)Molecules 29 05121 i017
(3h)		92%
8Molecules 29 05121 i018
(1c)		(2g)Molecules 29 05121 i019
(3i)		94%
9Molecules 29 05121 i020
(1d)		(2f)Molecules 29 05121 i021
(3j)		91%
10Molecules 29 05121 i022
(1e)		(2b)Molecules 29 05121 i023
(3k)		95%
11Molecules 29 05121 i024
(1f)		(2g)Molecules 29 05121 i025
(3l)		96%
12(1a)Molecules 29 05121 i026No reaction-
13(1a)Molecules 29 05121 i027No reaction-
14(1a)Molecules 29 05121 i028No reaction-
a Isolated yield based on aryl halide.
Table 3. Recyclability test in Sonogashira coupling.
Table 3. Recyclability test in Sonogashira coupling.
Molecules 29 05121 i029
Recycle1st2nd3rd4th5th6th7th
Yield a98%98%96%97%95%94%90%
a Isolated yield based on 2a.
Table 4. Click reaction using Fe3O4@PDA-Cys@Cu.
Table 4. Click reaction using Fe3O4@PDA-Cys@Cu.
Molecules 29 05121 i030
EntryXYZProductResult aResult b
1H4-BrBr4b80%95%
2H4-t-BuBr4c88%98%
3H4-FCl4d90%90%
4H4-CNCl4e85%90%
5H2,4-Cl2Cl4f95%96%
64-FHBr4g90%96%
74-C4H9HBr4h86%97%
84-OCH3HBr4i96%98%
94-NO2HBr4j90%91%
103-OHHBr4k88%95%
114-NO24-FCl4l88%92%
124-F2,4-Cl2Cl4m80%92%
133-CH34-t-BuBr4n96%97%
a Isolated yield based on benzyl halide using Fe3O4@PDA@Cu platform [results cited from reference [40]]. b Isolated yield based on benzyl halide using Fe3O4@PDA-Cys@Cu platform [this work].
Table 5. Reusability test using the Fe3O4@PDA@Cu and Fe3O4@PDA-Cys@Cu platforms.
Table 5. Reusability test using the Fe3O4@PDA@Cu and Fe3O4@PDA-Cys@Cu platforms.
Molecules 29 05121 i031
Recycling01st2nd3rd4th5th6th7th
Yield a98% (5 h)97% (7 h)72% (7 h)51% (7 h)----
Yield b99%99%96%96%95%95%95%90%
a Isolated yield of 4a (based on 2a) using Fe3O4@PDA@Cu platform. The number in parentheses indicates the reaction time. b Isolated yield of 4a (based on 2a) using Fe3O4@PDA-Cys@Cu platform. Each run was conducted in 5 h.
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Jo, Y.-J.; Park, S.-W.; Shin, U.S.; Kim, S.-H. Copper Catalysts Anchored on Cysteine-Functionalized Polydopamine-Coated Magnetite Particles: A Versatile Platform for Enhanced Coupling Reactions. Molecules 2024, 29, 5121. https://doi.org/10.3390/molecules29215121

AMA Style

Jo Y-J, Park S-W, Shin US, Kim S-H. Copper Catalysts Anchored on Cysteine-Functionalized Polydopamine-Coated Magnetite Particles: A Versatile Platform for Enhanced Coupling Reactions. Molecules. 2024; 29(21):5121. https://doi.org/10.3390/molecules29215121

Chicago/Turabian Style

Jo, Yu-Jeong, Seung-Woo Park, Ueon Sang Shin, and Seung-Hoi Kim. 2024. "Copper Catalysts Anchored on Cysteine-Functionalized Polydopamine-Coated Magnetite Particles: A Versatile Platform for Enhanced Coupling Reactions" Molecules 29, no. 21: 5121. https://doi.org/10.3390/molecules29215121

APA Style

Jo, Y.-J., Park, S.-W., Shin, U. S., & Kim, S.-H. (2024). Copper Catalysts Anchored on Cysteine-Functionalized Polydopamine-Coated Magnetite Particles: A Versatile Platform for Enhanced Coupling Reactions. Molecules, 29(21), 5121. https://doi.org/10.3390/molecules29215121

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