Advertisement

Polythiophene‐functionalized magnetic carbon nanotube-supported copper(I) complex: a novel and retrievable heterogeneous catalyst for the “Phosphine- and Palladium-Free” Suzuki–Miyaura cross-coupling reaction

  • Parisa Akbarzadeh
  • Nadiya KoukabiEmail author
  • Eskandar Kolvari
Original Article
  • 32 Downloads

Abstract

A simple preparation of catalysts with high catalytic activity and superior cycling stability is very desirable. In this contribution, magnetic carbon nanotube functionalized by polythiophene (CNT–Fe3O4–PTh) acts as an efficient and retrievable host for copper nanoparticles to prepare CNT–Fe3O4–PTh–Cu(I) as a nontoxic and inexpensive catalyst. FT-IR, TGA, EDX, VSM, XRD, FE-SEM, TEM, and AAS techniques were employed to characterize the structure of the synthesized magnetic heterogeneous nanocomposite. Thereafter, the catalytic application of the catalyst was evaluated for the phosphine- and palladium-free Suzuki–Miyaura cross-coupling reaction in water/ethanol as a green media in short reaction times with good to excellent yields. Various derivatives of biaryl compounds were synthesized by reaction of aryl halides and phenylboronic acid. Simple methodology and easy workup, short reaction times, elimination of volatile and toxic solvents, biocompatible reaction conditions, and high yields are some advantages of this protocol. Moreover, the catalyst showed a good reusability owing to its magnetic properties and was recycled several times without appreciable decrease in its catalytic efficiency.

Graphic abstract

Copper(I) nanoparticles supported on magnetic carbon nanotube functionalized by polythiophene (CNT–Fe3O4–PTh–Cu(I)), was prepared and used for ligand- and palladiumfree Suzuki–Miyaura cross-coupling reaction in water/ethanol as a green media in short reaction times with good to excellent yields. Reusability and stability tests demonstrated that the as prepared catalyst can be recycled with a negligible loss of its activity.

Keywords

Carbon nanotube Copper(I) nanocomposite Magnetic nanoparticles Polythiophene Suzuki–Miyaura cross-coupling reaction 

Notes

Acknowledgements

The authors gratefully acknowledge the Research Council of the Semnan University for the financial support of this work.

Supplementary material

11030_2019_10016_MOESM1_ESM.docx (1.2 mb)
Copies of 1H-NMR and 13C-NMR of some selected products (DOCX 1244 kb)

References

  1. 1.
    Fihri A, Bouhrara M, Nekoueishahraki B, Basset JM, Polshettiwar V (2011) Nanocatalysts for Suzuki cross-coupling reactions. Chem Soc Rev 40:5181–5203PubMedCrossRefGoogle Scholar
  2. 2.
    Beletskaya IP, Cheprakov AV (2000) The Heck reaction as a sharpening stone of palladium catalysis. Chem Rev 100:3009–3066PubMedCrossRefGoogle Scholar
  3. 3.
    Polshettiwar V, Molnár Á (2007) Silica-supported Pd catalysts for Heck coupling reactions. Tetrahedron 30:6949–6976CrossRefGoogle Scholar
  4. 4.
    Stanforth SP (1998) Catalytic cross-coupling reactions in biaryl synthesis. Tetrahedron 54:263–303CrossRefGoogle Scholar
  5. 5.
    Kim JH, Park JS, Chung HW, Boote BW, Lee TR (2012) Palladium nanoshells coated with self-assembled monolayers and their catalytic properties. RSC Adv 2:3968–3977CrossRefGoogle Scholar
  6. 6.
    Tamami B, Allahyari H, Farjadian F, Ghasemi S (2011) Synthesis and applications of poly (N-vinylimidazole) grafted silica-containing palladium nanoparticles as a new recyclable catalyst for Heck, Sonogashira and Suzuki coupling reactions. Iran Polym J 20:699–712Google Scholar
  7. 7.
    Wu XF, Anbarasan P, Neumann H, Beller M (2010) From noble metal to Nobel prize: palladium-catalyzed coupling reactions as key methods in organic synthesis. Angew Chem Int Ed 49:9047–9050CrossRefGoogle Scholar
  8. 8.
    Fürstner A, Leitner A (2001) General and user-friendly method for Suzuki reactions with aryl chlorides. Synlett 2001:0290–0292CrossRefGoogle Scholar
  9. 9.
    Sobhani S, Zeraatkar Z, Zarifi F (2015) Pd complex of an NNN pincer ligand supported on γ-Fe2O3@SiO2 magnetic nanoparticles: a new catalyst for heck, Suzuki and Sonogashira coupling reactions. New J Chem 39:7076–7085CrossRefGoogle Scholar
  10. 10.
    Saleem F, Rao GK, Singh P, Singh AK (2013) Chalcogen-dependent palladation at the benzyl carbon of 2, 3-Bis[(phenylchalcogeno) methyl] quinoxaline: palladium Complexes Catalyzing Suzuki–Miyaura coupling via palladium-chalcogen nanoparticles. Organometallics 32:387–395CrossRefGoogle Scholar
  11. 11.
    Kumar A, Rao GK, Saleem F, Kumar R, Singh AK (2014) Efficient catalysis of Suzuki–Miyaura CC coupling reactions with palladium (II) complexes of partially hydrolyzed bisimine ligands: a process important in environment context. J Hazard Mater 269:l9–17CrossRefGoogle Scholar
  12. 12.
    Mao J, Guo J, Fang F, Ji SJ (2008) Highly efficient copper (0)-catalyzed Suzuki–Miyaura cross-coupling reactions in reusable PEG-400. Tetrahedron 64:3905–3911CrossRefGoogle Scholar
  13. 13.
    Thathagar MB, Beckers J, Rothenberg G (2003) Combinatorial design of copper-based mixed nanoclusters: new catalysts for Suzuki cross-coupling. Adv Synth Catal 345:979–985CrossRefGoogle Scholar
  14. 14.
    Thapa S, Shrestha B, Gurung SK, Giri R (2015) Copper-catalysed cross-coupling: an untapped potential. Org Biomol Chem 13:4816–4827PubMedCrossRefPubMedCentralGoogle Scholar
  15. 15.
    Basnet P, Thapa S, Dickie DA, Giri R (2016) The copper-catalysed Suzuki–Miyaura coupling of alkylboron reagents: disproportionation of anionic (alkyl)(alkoxy) borates to anionic dialkylborates prior to transmetalation. Chem Commun 52:11072–11075CrossRefGoogle Scholar
  16. 16.
    Wang K, Yang L, Zhao W, Cao L, Sun Z, Zhang F (2017) A facile synthesis of copper nanoparticles supported on an ordered mesoporous polymer as an efficient and stable catalyst for solvent-free sonogashira coupling Reactions. Green Chem 19:1949–1957CrossRefGoogle Scholar
  17. 17.
    Ranu BC, Dey R, Chatterjee T, Ahammed S (2012) Copper nanoparticle-catalyzed carbon–carbon and carbon–heteroatom bond formation with a greener perspective. Chemsuschem 5:22–44PubMedCrossRefPubMedCentralGoogle Scholar
  18. 18.
    Yang CT, Zhang ZQ, Liu YC, Liu L (2011) Copper-catalyzed cross-coupling reaction of organoboron compounds with primary alkyl halides and pseudohalides. Angew Chem 123:3990–3993CrossRefGoogle Scholar
  19. 19.
    Colacino E, Daich L, Martinez J, Lamaty F (2007) Microwave-assisted copper-catalyzed Sonogashira reaction in PEG solvent. Synlett 2007:1279–1283CrossRefGoogle Scholar
  20. 20.
    Beletskaya IP, Cheprakov AV (2004) Copper in cross-coupling reactions: the post-Ullmann chemistry. Coord Chem Rev 248:2337–2364CrossRefGoogle Scholar
  21. 21.
    Xia X, Xie C, Cai S, Yang Z, Yang X (2006) Corrosion characteristics of copper microparticles and copper nanoparticles in distilled water. Corros Sci 48:3924–3932CrossRefGoogle Scholar
  22. 22.
    Yanase A, Komiyama H (1991) Real-time optical observation of morphological change of small supported copper particles during redox treatments. Surf Sci 248:20–26CrossRefGoogle Scholar
  23. 23.
    Hafez IH, Berber MR, Fujigaya T, Nakashima N (2017) High electronic conductivity and air stability of ultrasmall copper-metal nanoparticles supported on pyridine-based polybenzimidazole carbon nanotube composite. ChemCatChem 9:4282–4286CrossRefGoogle Scholar
  24. 24.
    Zhang HX, Siegert U, Liu R, Cai WB (2009) Facile fabrication of ultrafine copper nanoparticles in organic solvent. Nanoscale Res Lett 4:705PubMedPubMedCentralCrossRefGoogle Scholar
  25. 25.
    Cioffi N, Torsi L, Ditaranto N, Sabbatini L, Zambonin PG, Tantillo G, Traversa E (2004) Antifungal activity of polymer-based copper nanocomposite coatings. Appl Phys Lett 85:2417–2419CrossRefGoogle Scholar
  26. 26.
    Carswell AD, O’Rea EA, Grady BP (2003) Adsorbed surfactants as templates for the synthesis of morphologically controlled polyaniline and polypyrrole nanostructures on flat surfaces: from spheres to wires to flat films. J Am Chem Soc 125:14793–14800PubMedCrossRefPubMedCentralGoogle Scholar
  27. 27.
    Bora C, Pegu R, Saikia BJ, Dolui SK (2014) Synthesis of polythiophene/graphene oxide composites by interfacial polymerization and evaluation of their electrical and electrochemical properties. Polym Int 63:2061–2067CrossRefGoogle Scholar
  28. 28.
    Thathagar MB, Beckers J, Rothenberg G (2002) Copper-catalyzed Suzuki cross-coupling using mixed nanocluster catalysts. J Am Chem Soc 124:11858–11859PubMedCrossRefPubMedCentralGoogle Scholar
  29. 29.
    Fodor A, Hell Z, Pirault-Roy L (2014) Copper (II)-and palladium (II)-modified molecular sieve, a reusable catalyst for the Suzuki–Miyaura-coupling. Appl Catal A: Gen 484:39–50CrossRefGoogle Scholar
  30. 30.
    Wang B, Yang P, Ge ZW, Li CP (2015) A porous metal–organic framework as active catalyst for multiple C–N/C–C bond formation reactions. Inorg Chem Commun 61:13–15CrossRefGoogle Scholar
  31. 31.
    Miri SS, Khoobi M, Ashouri F, Jafarpour F, Ranjbar PR, Shafiee A (2015) Efficient C–C cross-coupling reactions by (isatin)-Schiff base functionalized magnetic nanoparticle-supported Cu(II) acetate as a magnetically recoverable catalyst. Turk J Chem 39:1232–1246CrossRefGoogle Scholar
  32. 32.
    Lamei K, Eshghi H, Bakavoli M, Rounaghi SA, Esmaeili E (2017) Carbon coated copper nanostructures as a green and ligand free nanocatalyst for Suzuki cross-coupling reaction. Catal Commun 92:40–45CrossRefGoogle Scholar
  33. 33.
    Ranjani G, Nagarajan R (2017) Insight into copper catalysis. in situ formed nano Cu2O in Suzuki–Miyaura cross-coupling of aryl/indolyl boronates. Org Lett 19:3974–3977PubMedCrossRefGoogle Scholar
  34. 34.
    Ghorbani-Choghamarani A, Derakhshan AA, Hajjami M, Rajabi L (2016) Copper-Schiff base alumoxane: a new and reusable mesoporous nano catalyst for Suzuki–Miyaura and Stille C–C cross-coupling reactions. RSC Adv 6:94314–94324CrossRefGoogle Scholar
  35. 35.
    Kour G, Gupta M, Vishwanathan B, Thirunavukkarasu K (2016) (Cu/NCNTs): a new high temperature technique to prepare a recyclable nanocatalyst for four component pyridine derivative synthesis and nitroarenes reduction. New J Chem 40:8535–8542CrossRefGoogle Scholar
  36. 36.
    Zhai Y, Dou Y, Zhao D, Fulvio PF, Mayes RT, Dai S (2011) Carbon materials for chemical capacitive energy storage. Adv Mater 23:4828–4850PubMedCrossRefPubMedCentralGoogle Scholar
  37. 37.
    Kim E, Jeong HS, Kim BM (2014) Studies on the functionalization of MWNTs and their application as a recyclable catalyst for CC bond coupling reactions. Catal Commun 46:71–74CrossRefGoogle Scholar
  38. 38.
    Bertolucci E, Bacsa R, Benyounes A, Raspolli-Galletti AM, Axet MR, Serp P (2015) Effect of the carbon support on the catalytic activity of ruthenium-magnetite catalysts for p-chloronitrobenzene hydrogenation. ChemCatChem 7:2971–2978CrossRefGoogle Scholar
  39. 39.
    Bagherzadeh M, Mortazavi-Manesh A (2016) Nanoparticle supported, magnetically separable manganese porphyrin as an efficient retrievable nanocatalyst in hydrocarbon oxidation reactions. RSC Adv 6:41551–41560CrossRefGoogle Scholar
  40. 40.
    Ódálaigh C, Corr SA, Gun’ko Y, Connon SJ (2007) A magnetic-nanoparticle-supported 4-N, N-dialkylaminopyridine catalyst: excellent reactivity combined with facile catalyst recovery and recyclability. Angew Chem Int Ed 46:4329–4332CrossRefGoogle Scholar
  41. 41.
    Kalidindi SB, Jagirdar BR (2012) Nanocatalysis and prospects of green chemistry. Chemsuschem 5:65–75PubMedCrossRefPubMedCentralGoogle Scholar
  42. 42.
    Lim CW, Lee IS (2010) Magnetically recyclable nanocatalyst systems for the organic reactions. Nano Today 5:412–434CrossRefGoogle Scholar
  43. 43.
    Koukabi N, Kolvari E, Zolfigol MA, Khazaei A, Shaghasemi BS, Fasahati B (2012) A magnetic particle-supported sulfonic acid catalyst: tuning catalytic activity between homogeneous and heterogeneous catalysis. Adv Synth Catal 354:2001–2008CrossRefGoogle Scholar
  44. 44.
    Koukabi N, Kolvari E, Khazaei A, Zolfigol MA, Shirmardi-Shaghasemi B, Khavasi HR (2011) Hantzsch reaction on free nano-Fe2O3 catalyst: excellent reactivity combined with facile catalyst recovery and recyclability. Chem Commun 47:9230–9232CrossRefGoogle Scholar
  45. 45.
    Akbarzadeh P, Koukabi N, Kolvari E (2019) Anchoring of triethanolamine–Cu (II) complex on magnetic carbon nanotube as a promising recyclable catalyst for the synthesis of 5-substituted 1H-tetrazoles from aldehydes. Mol Divers 1–15Google Scholar
  46. 46.
    Arghan M, Koukabi N, Kolvari E (2018) Mizoroki-Heck and Suzuki–Miyaura reactions mediated by poly(2-acrylamido-2-methyl-1-propanesulfonic acid)-stabilized magnetically separable palladium catalyst. Appl Organomet Chem 32:e4346CrossRefGoogle Scholar
  47. 47.
    Lotfi Z, Mousavi HZ, Sajjadi SM (2017) Magnetic carbon nanotubes modified with 1, 4-diazabicyclo [2.2.2] octane are a viable sorbent for extraction of selective serotonin reuptake inhibitors. Microchim Acta 184:1427–1436CrossRefGoogle Scholar
  48. 48.
    Mehdinia A, Khodaee N, Jabbari A (2015) Fabrication of graphene/Fe3O4@ polythiophene nanocomposite and its application in the magnetic solid-phase extraction of polycyclic aromatic hydrocarbons from environmental water samples. Anal Chim Acta 868:1–9PubMedCrossRefPubMedCentralGoogle Scholar
  49. 49.
    Lu MD, Yang SM (2005) Syntheses of polythiophene and titania nanotube composites. Synth Met 154:73–76CrossRefGoogle Scholar
  50. 50.
    Li J, Tang S, Lu L, Zeng HC (2007) Preparation of nanocomposites of metals, metal oxides, and carbon nanotubes via self-assembly. J Am Chem Soc 129:9401–9409PubMedCrossRefPubMedCentralGoogle Scholar
  51. 51.
    Sabaqian S, Nemati F, Nahzomi HT, Heravi MM (2018) Silver(I) dithiocarbamate on modified magnetic cellulose: synthesis, density functional theory study and application. Carbohydr Polym 184:221–230PubMedCrossRefPubMedCentralGoogle Scholar
  52. 52.
    Chidambaram S, Pari B, Kasi N, Muthusamy S (2016) ZnO/Ag heterostructures embedded in Fe3O4 nanoparticles for magnetically recoverable photocatalysis. J Alloys Compd 665:404–410CrossRefGoogle Scholar
  53. 53.
    Hemmati M, Rajabi M, Asghari A (2017) A twin purification/enrichment procedure based on two versatile solid/liquid extracting agents for efficient uptake of ultra-trace levels of lorazepam and clonazepam from complex bio-matrices. J Chromatogr A 1524:1–12PubMedCrossRefPubMedCentralGoogle Scholar
  54. 54.
    Hajipour AR, Hosseini SM, Mohammadsaleh F (2016) DABCO-functionalized silica–copper(I) complex: a novel and recyclable heterogeneous nanocatalyst for palladium-free Sonogashira cross-coupling reactions. New J Chem 40:6939–6945CrossRefGoogle Scholar
  55. 55.
    Singh VV, Singh AK (2015) Tetragonal Cu2Se nanoflakes: synthesis using selenated propylamine as Se source and activation of Suzuki and Sonogashira cross coupling reactions. Dalton Trans 44:725–732PubMedCrossRefPubMedCentralGoogle Scholar

Copyright information

© Springer Nature Switzerland AG 2019

Authors and Affiliations

  1. 1.Department of ChemistrySemnan UniversitySemnanIran

Personalised recommendations