Synlett 2013; 24(10): 1309-1310
DOI: 10.1055/s-0033-1338949
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© Georg Thieme Verlag Stuttgart · New York

Copper Ferrite (CuFe2O4) Nanoparticles

Reuben Hudson
McGill University, Department of Chemistry, 801 Sherbrooke Street West, Montreal, QC, H3A 0B8, Canada   Email: reuben.hudson@mail.mcgill.ca
› Author Affiliations
Further Information

Publication History

Publication Date:
17 May 2013 (online)

 
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Reuben Hudson was born on the coast of Maine, USA, in 1986. He received his B.A. in chemistry under the advisement of Professor Chris Smart at Vassar College, in Poughkeepsie, NY. Currently, he is working toward his Ph.D. at McGill University, Montreal, Canada, with the groups of Professors Chao-Jun Li and Audrey Moores. His work focuses on the use of easily recoverable heterogeneous catalysts for various organic transformations.

Introduction

Ferrite (Fe3O4) nanoparticles (NPs) have been used as a catalyst for many organic transformations[1] because their nano-scale size equates to a large surface area to volume ratio (meaning many accessible active sites).[2] Moreover, iron-based magnetic properties enable easy catalyst recovery by the application of an external magnet. The catalytic scope of iron, however, pales in comparison with that of copper. Therefore, by substituting copper within the crystal lattice, the catalytic scope is greatly expanded, while the means of easy magnetic recovery are retained. The resulting copper ferrite nanoparticles (CuFe2O4 NPs) contain copper(II) and iron(III) species. Such nanoparticles can be obtained by co-precipitation of copper(II) and iron(III) salts (Scheme [1]).[3] They are also commercially available. Herein, the catalytic scope of CuFe2O4 NPs is highlighted and reviewed.

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Scheme 1 Synthesis of CuFe2O4 NPs by co-precipitation[3]

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Abstracts

(A) Azide–Alkyne ‘Click’ Reaction

Under homogeneous copper(I) conditions, this reaction can occur at room temperature in water.[4] Under heterogeneous conditions, the reaction requires either 70 °C temperature[5] or the addition of a ligand such as 2,2-bipyridine.[6]

(B) C–C Cross-Coupling

Panda and co-workers[7] demonstrated a synergistic effect between copper and iron within the CuFe2O4 lattice to catalyze the coupling of terminal alkynes with aryl halides. Neither CuO NPs, nor Fe3O4 NPs alone, could catalyze the transformation as effectively.

(C) C–N Cross-Coupling

Panda and co-workers[8] again demonstrated a synergistic effect between copper and iron, this time in the CuFe2O4 NP-catalyzed coupling of N-heterocycles with aryl halides.

(D) C–O Cross-Coupling

The Sun group[9] effectively coupled aryl halides with phenols to generate the corresponding biaryl ethers by catalysis with CuFe2O4 nanoparticles.

(E) C–S Cross-Coupling

The coupling under basic conditions and elevated temperatures of aryl halides with either aromatic thiols or diaryl suphides afforded the corresponding diaryl sulphide in excellent yields. The catalytic efficiency of various [M]Fe2O4 nanoparticles were compared and M = copper was found to be the most reactive for this transformation.[10]

(F) C–Se Cross-Coupling

Various diaryl selenides were synthesized by the coupling of aryl halides with diaryl diselenides. The reaction required the use of a base and temperatures of 120˚C.[11]

(G) Sugar Deacylation

Various protected sugars were deacylated with copper ferrite nanoparticles under mild conditions. By altering the solvent and reducing the reaction time, selective deacylation at the anomeric position could be achieved.[12]

(H) A3 Coupling

The three-component, one-pot coupling of aldehyde, alkyne, and amine was reported. Although A3 coupling has already been achieved for Fe3O4 nanoparticles, substituting copper within the lattice enabled the use of milder conditions.[13]

(I) Biginelli Condensation

In another demonstration of a three-component one-pot reaction, the Biginelli condensation between an aldehyde, urea or thiourea, and β-ketoesters was achieved with CuFe2O4 NPs to afford the corresponding dihydropyrimidinones or dihydropyrimidinthiones.[14]

(J) Asymmetric Hydrosilylation

With the aid of a chiral BINAP ligand, CuFe2O4 NPs have catalyzed the asymmetric hydrosilylation of prochiral ketones, which afforded the corresponding alcohols upon TBAF workup.15�


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  • References

    • 1a Shi F, Tse MK, Pohl M.-M, Brückner A, Zhang S, Beller M. Angew. Chem. Int. Ed. 2007; 46: 8866
    • 1b Rajabi F, Karimi N, Saidi MR, Primo A, Varma RS, Luque R. Adv. Synth. Catal. 2012; 354: 1707
    • 1c Zeng T, Song G, Moores A, Li CJ. Synlett 2010; 2002
    • 1d Zeng TQ, Chen W.-W, Cirtiu CM, Moores A, Song GH, Li CJ. Green Chem. 2010; 12: 570
    • 1e Sreedhar B, Kumar AS, Reddy PS. Tetrahedron Lett. 2010; 51: 1891
    • 1f Reddy BV. S, Krishna AS, Ganesh AV, Kumar AS. Tetrahedron Lett. 2011; 52: 1359
    • 1g Firouzabadi H, Iranpoor N, Gholinejad M, Hoseini J. Adv. Synth. Catal. 2011; 353: 125
  • 2 Yan N, Xiao C, Kou Y. Coord. Chem. Rev. 2010; 254: 1179
  • 3 Mahmoodi NM. Desalination 2011; 279: 332
    • 4a Tornøe CW, Christensen C, Meldal M. J. Org. Chem. 2002; 67: 3057
    • 4b Rostovtsev VV, Green LG, Fokin VV, Sharpless KB. Angew. Chem. Int. Ed. 2002; 41: 2596
  • 5 Kumar BS. P. A, Reddy KH. V, Madhav B, Ramesh K, Nageswar YV. D. Tetrahedron Lett. 2012; 53: 4595
  • 6 Ishikawak S, Hudson R, Moores A, Li C.-J. Heterocycles 2012; 86: 1023
  • 7 Panda N, Jena AK, Mohapatra S. Chem. Lett. 2011; 40: 956
  • 8 Panda N, Jena AK, Mohapatra S, Rout SR. Tetrahedron Lett. 2011; 51: 1924
  • 9 Zhang R, Liu J, Wang S, Niu J, Xia C, Sun W. ChemCatChem 2011; 3: 146
  • 10 Swapna K, Murthy SN, Jyothi MT, Nageswar YV. D. Org. Biomol. Chem. 2011; 5989
  • 11 Swapna K, Murthy SN, Nageswar YV. D. Eur. J. Org. Chem. 2011; 1940
  • 12 Tasca JE, Ponzinibbio A, Diaz G, Bravo RD, Lavat A, González MG. Top. Catal. 2010; 1087
  • 13 Kantam ML, Yadav J, Laha S, Jha S. Synlett 2009; 1791
  • 14 Hudson R, Silverman J, Li C.-J, Moores A Proceedings of the 3rd International Conference on Nanotechnology; Montreal, QC, Canada, 2012; Paper No. 318.
  • 15 Kantam ML, Yadav Y, Laha S, Srinivas P, Sreedhar B, Figueras F. J. Org. Chem. 2009; 74: 4608

  • References

    • 1a Shi F, Tse MK, Pohl M.-M, Brückner A, Zhang S, Beller M. Angew. Chem. Int. Ed. 2007; 46: 8866
    • 1b Rajabi F, Karimi N, Saidi MR, Primo A, Varma RS, Luque R. Adv. Synth. Catal. 2012; 354: 1707
    • 1c Zeng T, Song G, Moores A, Li CJ. Synlett 2010; 2002
    • 1d Zeng TQ, Chen W.-W, Cirtiu CM, Moores A, Song GH, Li CJ. Green Chem. 2010; 12: 570
    • 1e Sreedhar B, Kumar AS, Reddy PS. Tetrahedron Lett. 2010; 51: 1891
    • 1f Reddy BV. S, Krishna AS, Ganesh AV, Kumar AS. Tetrahedron Lett. 2011; 52: 1359
    • 1g Firouzabadi H, Iranpoor N, Gholinejad M, Hoseini J. Adv. Synth. Catal. 2011; 353: 125
  • 2 Yan N, Xiao C, Kou Y. Coord. Chem. Rev. 2010; 254: 1179
  • 3 Mahmoodi NM. Desalination 2011; 279: 332
    • 4a Tornøe CW, Christensen C, Meldal M. J. Org. Chem. 2002; 67: 3057
    • 4b Rostovtsev VV, Green LG, Fokin VV, Sharpless KB. Angew. Chem. Int. Ed. 2002; 41: 2596
  • 5 Kumar BS. P. A, Reddy KH. V, Madhav B, Ramesh K, Nageswar YV. D. Tetrahedron Lett. 2012; 53: 4595
  • 6 Ishikawak S, Hudson R, Moores A, Li C.-J. Heterocycles 2012; 86: 1023
  • 7 Panda N, Jena AK, Mohapatra S. Chem. Lett. 2011; 40: 956
  • 8 Panda N, Jena AK, Mohapatra S, Rout SR. Tetrahedron Lett. 2011; 51: 1924
  • 9 Zhang R, Liu J, Wang S, Niu J, Xia C, Sun W. ChemCatChem 2011; 3: 146
  • 10 Swapna K, Murthy SN, Jyothi MT, Nageswar YV. D. Org. Biomol. Chem. 2011; 5989
  • 11 Swapna K, Murthy SN, Nageswar YV. D. Eur. J. Org. Chem. 2011; 1940
  • 12 Tasca JE, Ponzinibbio A, Diaz G, Bravo RD, Lavat A, González MG. Top. Catal. 2010; 1087
  • 13 Kantam ML, Yadav J, Laha S, Jha S. Synlett 2009; 1791
  • 14 Hudson R, Silverman J, Li C.-J, Moores A Proceedings of the 3rd International Conference on Nanotechnology; Montreal, QC, Canada, 2012; Paper No. 318.
  • 15 Kantam ML, Yadav Y, Laha S, Srinivas P, Sreedhar B, Figueras F. J. Org. Chem. 2009; 74: 4608

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Scheme 1 Synthesis of CuFe2O4 NPs by co-precipitation[3]