Skip to main content
SpringerLink
Log in

Facile synthesis of hairy microparticle-/nanoparticle-supported MacMillan and its application to Diels–Alder reaction in water

  • Original Contribution
  • Published:
Colloid and Polymer Science Aims and scope Submit manuscript

Abstract

Herein, a series of hairy microparticle-/nanoparticle-supported MacMillan was successfully synthesized by RAFT precipitation polymerization combination with surface-initiated RAFT polymerization. The research’s interest was aimed at achieving a significant enhancement of the catalytic performance which was achieved due to the changes of the polymer particle size, the molecular weight of the grafting polymer brushes, as well as the grafting polymer structure. The results showed that nanoeffect was the key to affect the catalytic activity and selectivity of catalyst system. The hairy nanoparticle had good dispersion in the reaction media and exhibited better catalytic activity and selectivity than hairy microspheres. In addition, the brush structure can be modified by grafting copolymerization with acrylamide which had the synergistic effect to effectively promote the catalyst reaction. The more significant advantages of the hairy nanoparticle-supported MacMillan were that it can effectively catalyze a representative asymmetric Diels–Alder reaction between cyclopentadiene and cinnamaldehyde in pure water and can be recycled five times while maintaining activity and selectivity.

Graphical abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Chu Q, Zhang W, Curran DP (2006) A recyclable fluorous organocatalyst for Diels–Alder reactions. Tetrahedron Lett 47:9287–9290

    Article  CAS  Google Scholar 

  2. Guizzetti S, Benaglia M, Siegel JS (2012) Poly (methylhydrosiloxane)-supported chiral imidazolinones: new versatile, highly efficient and recyclable organocatalysts for stereoselective Diels–Alder cycloaddition reactions. Chem Commun 48:3188–3190

    Article  CAS  Google Scholar 

  3. Xie JW, Yue L, Chen W, Du W, Zhu J, Deng JG, Chen YC (2007) Highly enantioselective Michael addition of cyclic 1, 3-dicarbonyl compounds to α,β-unsaturated ketones. Org Lett 9:413–415

    Article  CAS  Google Scholar 

  4. Chen XH, Wei Q, Luo SW, Xiao H, Gong LZ (2009) Organocatalytic synthesis of spiro [pyrrolidin-3, 3′-oxindoles] with high enantiopurity and structural diversity. J Am Chem Soc 131:13819–13825

    Article  CAS  Google Scholar 

  5. Bandini M, Fagioli M, Melchiorre P, Melloni A, Umani-Ronchi A (2003) Catalytic enantioselective conjugate addition of indoles to simple α,β-unsaturated ketones. Tetrahedron Lett 44:5843–5846

    Article  CAS  Google Scholar 

  6. Bandini M, Fagioli M, Garavelli M, Melloni A, Trigari V, Umani-Ronchi A (2004) Can simple enones be useful partners for the catalytic stereoselective alkylation of indoles. J Org Chem 69:7511–7518

    Article  CAS  Google Scholar 

  7. Moore BL, Lu A, Longbottom DA, O’Reilly RK (2013) Immobilization of MacMillan catalyst via controlled radical polymerization:catalytic activity and reuse. Polym Chem 4:2304–2312

    Article  CAS  Google Scholar 

  8. Kristensen TE, Vestli K, Jakobsen MG, Hansen FK, Hansen T (2010) A general approach for preparation of polymer-supported chiral organocatalysts via acrylic copolymerization. J Org Chem 75:1620–1629

    Article  CAS  Google Scholar 

  9. Selkälä SA, Tois J, Pihko PM, Koskinen AMP (2002) Asymmetric organocatalytic Diels–Alder reactions on solid support. Adv Synth Catal 344:941–945

    Article  Google Scholar 

  10. Benaglia M, Celentano G, Cinquini M, Puglisi A, Cozzi F (2002) Poly (ethylene glycol)-supported chiral imidazolidin-4-one: an efficient organic catalyst for the enantioselective Diels–Alder cycloaddition. AdvSynthCatal 344:149–152

    CAS  Google Scholar 

  11. Zhang YG, Zhao L, Lee SS, Ying JY (2006) Enantioselective catalysis over chiral imidazolidin-4-one immobilized on siliceous and polymer-coated mesocellular foams. Adv Synth Catal 348:2027–2032

    Article  CAS  Google Scholar 

  12. Haraguchi N, Takemura Y, Itsuno S (2010) Novel polymer-supported organocatalyst via ion exchange reaction: facile immobilization of chiral imidazolidin-4-one and its application to Diels–Alder reaction. Tetrahedron Lett 51:1205–1208

    Article  CAS  Google Scholar 

  13. Riente P, Yadav J, Pericàs MA (2012) A click strategy for the immobilization of MacMillan organocatalysts onto polymers and magnetic nanoparticles. Org Lett 14:3668–3671

    Article  CAS  Google Scholar 

  14. Shi JY, Wang CA, Li ZJ, Wang Q, Zhang Y, Wang W (2011) Heterogeneous organocatalysis at work: functionalization of hollow periodic mesoporous organosilica spheres with MacMillan catalyst. Chem A Eur J 17:6206–6213

    Article  CAS  Google Scholar 

  15. Lu A, Smart TP, Epps IIITH, Longbottom DA, O’Reilly RK (2011) L -proline functionalized polymers prepared by RAFT polymerization and their assemblies as supported organocatalysts. Macromolecules 44:7233–7241

    Article  CAS  Google Scholar 

  16. Hasan OE, Niyazi B (2016) Preparation of PANI coated polymer microspheres and their use as Michael acceptor for direct immobilization of amines and amino acids. React Funct Polym 99:88–94

    Article  Google Scholar 

  17. Carrot G, Rutot-Houzé D, Pottier A, Degée P, Hilborn J, Dubois P (2002) Surface-initiated ring-opening polymerization: a versatile method for nanoparticle ordering. Macromolecules 35:8400–8404

    Article  CAS  Google Scholar 

  18. Chen XY, Randall DP, Perruchot C, Watts JF, Patten TE, von Werne T, Armes SP (2003) Synthesis and aqueous solution properties of polyelectrolyte-grafted silica particles prepared by surface-initiated atom transfer radical polymerization. J Colloid Interface Sci 257:56–64

    Article  CAS  Google Scholar 

  19. ParvoleJ BL, Montfort JP (2002) Formation of polyacrylate brushes on silica surfaces. Polym Int 51:1111–1116

    Article  Google Scholar 

  20. Parvole J, Laruelle G, Guimon C, Francoisl J, Billon L (2003) Initiator-grafted silica particles for controlled free radical polymerization: influence of the initiator structure on the grafting density. Macromol Rapid Commun 24:1074–1078

    Article  CAS  Google Scholar 

  21. Parvole J, Montfort JP, Billon L (2004) Formation of inorganic/organic nanocomposites by Nitroxide-mediated polymerization in bulk using a bimolecular system. Macromol Chem Phys 205:1369–1378

    Article  CAS  Google Scholar 

  22. Bartholome C, Beyou E, Bourgeat-Lami E, Chaumont P, Zydowicz N (2003) Nitroxide-mediated polymerizations from silica nanoparticle surfaces:“graft from” polymerization of styrene using a triethoxysilyl-terminated alkoxyamine initiator. Macromolecules 36:7946–7952

    Article  CAS  Google Scholar 

  23. Inoubli R, Dagréou S, Khoukh A, Roby F, Peyrelasse J, Billon L (2005) ‘Graft from’ polymerization on colloidal silica particles: elaboration of alkoxyamine grafted surface by in situ trapping of carbon radicals. Polymer 46:2486–2496

    Article  CAS  Google Scholar 

  24. Li XJ, Chen MQ, Yang BL, Zhang SL, Jia XB, Hu ZG (2014) Combining RAFT precipitation polymerization and surface-initiated RAFT polymerization: an efficient approach to prepare hairy particles-supported proline. RSC Adv 4:43278–43285

    Article  CAS  Google Scholar 

  25. Li XJ, Yang BL, Jia XB, Hu ZG (2015) Temperature-responsive hairy particle-supported proline for direct asymmetric aldol reaction in water 5:89149–89156.

  26. Pan GQ, Zu BY, Guo XZ, Zhang Y, Li CX, Zhang HQ (2009) Preparation of molecularly imprinted polymer microspheres via reversible addition–fragmentation chain transfer precipitation polymerization. Polymer 50:2819–2825

    Article  CAS  Google Scholar 

  27. Zhang H (2013) Controlled/“living” radical precipitation polymerization: a versatile polymerization technique for advanced functional polymers. Eur Polym J l49:579–600

    Article  Google Scholar 

  28. Wackerlig J, Lieberzeit PA (2015) Molecularly imprinted polymer nanoparticles in chemical sensing-synthesis, characterisation and application. Sensors Actuators B 207:144–157

    Article  CAS  Google Scholar 

  29. Ling Y, Zhuan ZS, Li CM (2015) Atom transfer radical polymerization to fabricate monodisperse poly[glycidyl methacrylate-co-poly (ethylene glycol) methacrylate] microspheres and its application for protein affinity purification. J Colloid Interface Sci 453:151–158

    Article  Google Scholar 

  30. Fujii S, Aono K, Suzaki M, Hamasaki S, Yusa S, Nakamura Y (2012) pH-responsive hairy particles synthesized by dispersion polymerization with a macroinitiator as an inistab and their use as a gas-sensitive liquid marble stabilizer. Macromolecules 45:2863–2873

    Article  CAS  Google Scholar 

  31. Li CY, Zhao B, Zhu L (2014) Hairy particles: theory, synthesis, behavior, and applications. J Polym Sci B Polym Phys 52:1581–1582

    Article  CAS  Google Scholar 

  32. Peng F, Shao Z (2008) Advances in asymmetric organocatalytic reactions catalyzed by chiral primary amines. J Mol Catal A Chem l285:1–13

    Article  Google Scholar 

  33. Chiroli V, Benaglia M, Puglisi A, Porta R, Jumde RP, Mandoli A (2014) A chiral organocatalytic polymer-based monolithic reactor. Green Chem 16:2798–2806

    Article  CAS  Google Scholar 

  34. Otto S, Engberts JBFN (1999) A systematic study of ligand effects on a Lewis-acid-catalyzed Diels-Alder reaction in water. J Am Chem Soc 121:6798–6806

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No.21204019), the Post-doctoral Foundation of China (No.2012M521398), the Post-doctoral Foundation of Henan Province and the International Cooperation Project of Henan Province (No.134300510055), and the Henan Normal University Youth Backbone Teacher Foundation.

Author information

Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, the Key Laboratory of Green Chemical Media and Reactions, State Education Ministry of China, Henan Normal University, Xinxiang, 453007, People’s Republic of China

    Xinjuan Li, Beilei Yang, Suli Zhang, Xianbin Jia & Zhiguo Hu

Authors
  1. Xinjuan Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Beilei Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Suli Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xianbin Jia
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Zhiguo Hu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Xinjuan Li or Zhiguo Hu.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Li, X., Yang, B., Zhang, S. et al. Facile synthesis of hairy microparticle-/nanoparticle-supported MacMillan and its application to Diels–Alder reaction in water. Colloid Polym Sci 295, 573–582 (2017). https://doi.org/10.1007/s00396-017-4032-x

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00396-017-4032-x

Keywords

Search

Navigation