Elsevier

Journal of Organometallic Chemistry

Volume 897, 1 October 2019, Pages 236-246
Journal of Organometallic Chemistry

Copper-catalyzed Mizoroki-Heck coupling reaction using an efficient and magnetically reusable Fe3O4@SiO2@PrNCu catalyst

https://doi.org/10.1016/j.jorganchem.2019.06.029Get rights and content

Highlights

  • An organometallic heterogeneous and magnetically reusable catalyst was designed.

  • Our magnetite-based copper catalyst is an alternative to various palladium catalysts.

  • Copper is an eco-friendly and low-cost transition-metal nanoparticle than palladium.

  • The Fe3O4@SiO2@PrNCu catalyst was utilized for both Heck and Ullmann coupling reactions.

  • Heck and Ullmann coupling reactions both were performed in water reaction medium.

Abstract

This study intends to design and prepare a new magnetic copper catalyst and its activity was assessed by carbon-carbon coupling reactions. For this purpose, 1-[3-(trimethoxysilyl) propyl] urea (TMSPU), hydrazine and CuI were used sequentially to modify Fe3O4@SiO2 core-shell magnetic nanoparticles to obtain an efficient magnetic transition metal catalyst. Various analytical techniques were used to characterize the catalyst to show that the achieved structure and its properties are well-suited for coupling reactions. Finally, Mizoroki-Heck and Ullmann coupling reactions were performed using Fe3O4@SiO2@PrNCu catalyst. The new catalyst offer simple synthetic procedure, convenient use for routine casework and low price. The Fe3O4@SiO2@PrNCu catalyst was easily separated by means of a permanent and ordinary magnet and the recovered catalyst was reused in six cycles without any significant loss of activity.

Introduction

Regarding both industrial and synthetic point of views, transition-metal catalyzed carbon–carbon coupling reaction is a fundamental and challenging process since substitution reactions can occur on planar centers [1]. Carbon–carbon coupling reactions are included broadly in the synthetic procedures of valuable compounds such as various polymers, agrochemicals, dyes, organic conductors/semi-conductors and pharmaceutical intermediates [2,3]. Although our predecessors developed kinds of coupling reactions in recent decades but for large scale applications significant concern and drawbacks of this type of chemistry still remained that are the costs of the metal and ligand as well as the need for fully removing the metal from the final products.

So to overcome these drawbacks, as the first step, due to the high surface to volume ratios and very active surface atoms, transition-metal nanoparticles are very attractive catalysts compared to bulk catalysts [4]. Also, the design and/or utilization of organic ligands with carefully-placed binding sites offer great potential for the manufacture of complexes with novel architectures. In this regard, several chelators such as diamines, amino acids, 1,10-phenantrolines, diols and other nitrogen-, phosphorus- and oxygen-containing ligands are of a high interest because of their complexation and the chelation affinity [5]. Therefore, using different grafted electron-rich ligands in order to anchor the transition-metal nanoparticles, can address the second draw-back. Finally, to achieve optimal recyclability of the catalytic systems various studies on the magnetic character and catalytic applicability of the FeM magnetic nanoparticles were considered to overcome the third drawback [6]. In this case, hybrid organic–inorganic materials based on Fe3O4@SiO2 core–shell magnetic nanoparticles as special immobilizing carrier of the catalyst’ active sites have made significant contribution to current researches [[6], [7], [8]]. This is due to their inherent properties such as easy renewability and recovery by magnetic separation, thermal stability against degradation, large surface area and higher loading of metal-ligand complexes. The recent demand for low-cost and sustainable reaction procedures made many researchers turn their attention to design the new copper-mediated coupling reactions [5,9]. Among the carbon–carbon coupling reactions, Ullmann coupling of aryl halides offers resourceful ways of large-scale constructing biaryl units in some industrial processes [5,10]. While significant improvement in this area has been made, using a variety of transition-metal catalysts, the great numbers of reported Ullmann protocols are still homogeneous and the effective reports on heterogeneous and recyclable catalytic methods are inadequate [5,11]. Therefore, there has been remarkable attention in developing novel heterogeneous catalytic systems for this process with efficient reusability while preserving the basic activity of the catalytic active sites. In order to identify a robust and easily prepared system to catalyze carbon–carbon bond-forming reactions, we have designed, prepared and characterized Fe3O4@SiO2@PrNCu as an active heterogeneous magnetic catalyst (Scheme 1) and investigate its applicability in Ullmann carbon–carbon coupling reaction.

Section snippets

Generals

All the chemicals used in our prepared magnetic transition-metal catalyst achieved from several accomplished experiments were purchased at Merck and Aldrich Chemical Companies. The magnetic transition-metal catalyst was characterized by means of powder X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transformed infrared spectroscopy (FT-IR) and energy dispersive X-ray analysis (EDX). FT-IR spectrum was acquired with an ABB Bomem Model FTLA 2000 spectrophotometer using

Results and discussion

To prove the preparation of the Fe3O4@SiO2@PrNCu magnetic transition-metal catalyst successfully, the prepared catalyst was characterized by FT-IR (Fig. 1). In detail, in Fig. 1 the strong band appeared at around 587 cm−1 corresponded to characteristic peak of Fe–O vibrations in the Fe3O4 magnetic nanoparticles [12]. In terms of silica core-shell, Fe3O4@SiO2, the weak band around 800 cm−1 in FT-IR spectrum (Fig. 1), which was the characteristic peak of Si–O–Fe, implied that the siliceous

Conclusions

In summary, this paper has brought into our attention a preparation procedure of a novel magnetic transition-metal catalyst through co-precipitation and sol-gel experimental methods for application in carbon-carbon coupling reactions.

Magnetic behaviour of the catalyst besides the use of an electron-rich guanidine like bidentate ligand in the structure of catalyst improve the recovery and reusability of the catalyst and prevent any leaching of the transition metal active sites. In other words,

Acknowledgment

This work was supported by the Research Council of the Tarbiat Modares University and the Iran National Science Foundation (INSF, Grant No. 94028939).

References (18)

  • C. Sambiagio et al.

    Chem. Soc. Rev.

    (2014)
    H. Lin et al.

    Org. Prep. Proced. Int.

    (2013)
    S. Monda

    ChemTexts

    (2016)
  • L. Yin et al.

    Chem. Rev.

    (2007)
  • A.F.P. Biajoli et al.

    J. Braz. Chem. Soc.

    (2014)
    Q. Yang et al.

    Macromolecules

    (2009)
    V.L. Budarin et al.

    Curr. Org. Synth.

    (2010)
  • C. Torborg et al.

    Adv. Synth. Catal.

    (2009)
    T.-S. Jo et al.

    J. Am. Chem. Soc.

    (2009)
  • X. Liu et al.

    ACS Catal.

    (2018)
    R. Narayanan et al.

    J. Phys. Chem. B

    (2005)
    L.D. Pachon et al.

    Appl. Organomet. Chem.

    (2008)
  • I.P. Beletskaya et al.

    Coord. Chem. Rev.

    (2004)
    S.V. Ley et al.

    Angew. Chem. Int. Ed.

    (2003)
    K. Kunz et al.

    Synlett

    (2003)
    F. Monnier et al.

    Angew. Chem. Int. Ed.

    (2008)
    G. Evano et al.

    Chem. Rev.

    (2008)
    A. Klapars et al.

    J. Am. Chem. Soc.

    (2002)
    J.C. Antilla et al.

    J. Am. Chem. Soc.

    (2002)
    F.Y. Kwong et al.

    Org. Lett.

    (2003)
    D. Ma et al.

    Org. Lett.

    (2003)
    B. de Lange et al.

    Synlett

    (2006)
    A. Shafir et al.

    J. Am. Chem. Soc.

    (2006)
    A. Ouali et al.

    Organometallics

    (2007)
  • R.B.N. Baig et al.

    Chem. Commun.

    (2013)
    Q. Dong et al.

    Chem. Soc. Rev.

    (2018)
    Zh Meng et al.

    Nanoscale

    (2017)
    Zh Meng et al.

    Sci. China. Mater.

    (2019)
    Zh Meng et al.

    J. Organomet. Chem.

    (2017)
    Q. Dong et al.

    Adv. Funct. Mater.

    (2014)
    Q. Dong et al.

    Adv. Mater.

    (2012)
    K. Liu et al.

    Angew. Chem. Int. Ed.

    (2008)
  • V. Polshettiwar et al.

    Chem. Rev.

    (2011)
  • S. Shylesh et al.

    Angew. Chem. Int. Ed.

    (2010)
There are more references available in the full text version of this article.

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