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Synlett 2014; 25(11): 1534-1538
DOI: 10.1055/s-0033-1341248
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© Georg Thieme Verlag Stuttgart · New York

Synthesis of Pyridine- and 2-Oxazoline-Functionalized Vinyl Polymers by Alane-Based Frustrated Lewis Pairs

Jianghua He
a   Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523-1872, USA   Fax: +1(970)4911801   Email: eugene.chen@colostate.edu
,
Yuetao Zhang
a   Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523-1872, USA   Fax: +1(970)4911801   Email: eugene.chen@colostate.edu
b   State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, P. R. of China
,
Eugene Y.-X. Chen*
a   Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523-1872, USA   Fax: +1(970)4911801   Email: eugene.chen@colostate.edu
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Further Information

Publication History

Received: 16 February 2014

Accepted after revision: 04 April 2014

Publication Date:
28 April 2014 (online)

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Abstract

Reported herein is the first example of polymerization of polar vinyl monomers bearing the C=C–C=N functionality by Frustrated Lewis pairs (FLPs). In particular, FLPs based on Al(C6F5)3 and N-heterocyclic carbenes rapidly convert 2-vinyl pyridine and 2-isopropenyl-2-oxazoline into medium to high molecular weight, N-functionalized vinyl polymers. Activated monomer-alane adduct 1 and initiated zwitterionic intermediate 2 have been isolated and structurally characterized, providing strong evidence for the proposed bimolecular, activated monomer polymerization mechanism.

Key words

frustrated Lewis pairs - polymers - pyridines - nitrogen - monomers - polymerization

Supporting Information

    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
  • Supporting Information
 

  • References and Notes


      • For selected reviews, see:
    • 1a Frustrated Lewis Pairs I & II. In Topics in Current Chemistry. Vols. 332 & 334. Stephan DW, Erker G. Springer; New York: 2013
      Google Scholar
    • 1b Erker G. Pure Appl. Chem. 2012; 84: 2203
      Crossref
    • 1c Stephan DW. Org. Biomol. Chem. 2012; 10: 5740
      Crossref
    • 1d Erker G. Dalton Trans. 2011; 40: 7475
      Crossref
    • 1e Stephan DW, Erker G. Angew. Chem. Int. Ed. 2010; 49: 46
      Crossref
    • 1f Stephan DW. Dalton Trans. 2009; 3129
    • 1g Stephan DW. Org. Biomol. Chem. 2008; 6: 1535
      Crossref

      For selected recent examples, see:
    • 2a Hounjet LJ, Bannwarth C, Garon CN, Caputo CB, Grimme S, Stephan DW. Angew. Chem. Int. Ed. 2013; 52: 7492
      Crossref
    • 2b Ménard G, Hatnean JA, Cowley HJ, Lough AJ, Rawson JM, Stephan DW. J. Am. Chem. Soc. 2013; 135: 6446
      Crossref
    • 2c Dobrovetsky R, Stephan DW. J. Am. Chem. Soc. 2013; 135: 4974
      Crossref
    • 2d Chernichenko K, Madarász A, Pápai I, Nieger M, Leskelä M, Repo T. Nat. Chem. 2013; 5: 718
      Crossref
    • 2e Sajid M, Elmer L.-M, Rosorius C, Daniliuc CG, Grimme S, Kehr G, Erker G. Angew. Chem. Int. Ed. 2013; 52: 2243
      Crossref
    • 2f Sajid M, Kehr G, Wiegand T, Eckert H, Schwickert C, Pöttgen R, Cardenas AJ. P, Warren TH, Fröhlich R, Daniliuc CG, Erker G. J. Am. Chem. Soc. 2013; 135: 8882
      Crossref
    • 2g Appelt C, Slootweg JC, Lammertsma K, Uhl W. Angew. Chem. Int. Ed. 2013; 52: 4256
      Crossref
  • 3 Chen EY.-X. Top. Curr. Chem. 2013; 334: 239
    • 4a Zhang Y, Miyake GM, John MG, Falivene L, Caporaso L, Cavallo L, Chen EY.-X. Dalton Trans. 2012; 41: 9119
      CrossrefPubMed
    • 4b Zhang Y, Miyake GM, Chen EY.-X. Angew. Chem. Int. Ed. 2010; 49: 10158
      CrossrefPubMed
  • 5 Piedra-Arroni E, Ladavière C, Amgoune A, Bourissou D. J. Am. Chem. Soc. 2013; 135: 13306
  • 6 Sajid M, Stute A, Cardenas AJ. P, Culotta BJ, Hepperle JA. M, Warren TH, Schirmer B, Grimme S, Studer A, Daniliuc CG, Fröhlich R, Petersen JL, Kehr G, Erker G. J. Am. Chem. Soc. 2012; 134: 10156
    Crossref
  • 7 Xu T, Chen EY.-X. J. Am. Chem. Soc. 2014; 136: 1774
    CrossrefPubMed
    • 8a Barz M, Luxenhofer R, Zentel R, Vicent MJ. Polym. Chem. 2011; 2: 1900
      Crossref
    • 8b Luxenhofer R, Sahay G, Schulz A, Alakhova D, Bronich TK, Jordan R, Kabanov AV. J. Controlled Release 2011; 153: 73
      Crossref
    • 8c Viegas TX, Bentley MD, Harris JM, Fang Z, Yoon K, Dizman B, Weimer R, Mero A, Pasut G, Veronese FM. Bioconjugate Chem. 2011; 22: 976
      CrossrefPubMed
    • 8d Knop K, Hoogenboom R, Fischer D, Schubert US. Angew. Chem. Int. Ed. 2010; 49: 6288
      CrossrefPubMed
    • 8e Luxenhofer R, Schulz A, Roques C, Li S, Bronich TK, Batrakova EV, Jordan R, Kabanov AV. Biomaterials 2010; 31: 4972
      Crossref
    • 8f Schlaad H, Diehl C, Gress A, Meyer M, Demirel AL, Nur Y, Bertin A. Macromol. Rapid Commun. 2010; 31: 511
      Crossref
    • 8g Hoogenboom R. Angew. Chem. Int. Ed. 2009; 48: 7978
      Crossref
    • 8h Adams N, Schubert US. Adv. Drug Delivery Rev. 2007; 59: 1504
      CrossrefPubMed
    • 8i Tomalia DA, Thill BP, Fazio MJ. Polym. J. 1980; 12: 661
      Crossref
    • 9a Weber C, Neuwirth T, Kempe K, Ozkahraman B, Tamahkar E, Mert H, Becer CR, Schubert US. Macromolecules 2012; 45: 20
      Crossref
    • 9b Zhang N, Huber S, Schulz A, Luxenhofer R, Jordan R. Macromolecules 2009; 42: 2215
      Crossref
  • 10 Tomalia DA, Thill BP, Fazio MJ. Polym. J. 1980; 12: 661
    Crossref
  • 11 Zhang N, Salzinger S, Soller BS, Rieger B. J. Am. Chem. Soc. 2013; 135: 8810
    Crossref
  • 12 Kaneko H, Nagae H, Tsurugi H, Mashima K. J. Am. Chem. Soc. 2011; 133: 19626
    Crossref
  • 13 Inoue and co-workers first reported the concept of acceleration in anionic polymerization of MMA via steric separation of the nucleophile and the bulky aluminum Lewis acid. See: Kuroki M, Watanabe T, Aida T, Inoue S. J. Am. Chem. Soc. 1991; 113: 6903
  • 14 See the Supporting Information for experimental and characterization details.
  • 15 Chakraborty D, Chen EY.-X. Inorg. Chem. Commun. 2002; 5: 698
    Crossref
  • 16 Selected crystallographic data for 1: C25H7AlF15N, monoclinic, space group P2(1)/c, a = 10.6644(4) Å, b = 14.0645(5) Å, c = 16.5182(6) Å, β = 107.349(2)°, V = 2364.84(15) Å3, Z = 4, D calcd = 1.779 Mg/m3, GOF = 1.051, R 1 = 0.0243 [I >2σ(I)], wR2 = 0.0659. CCDC 972837 contains the supplementary crystallographic data for this structure.
  • 17 Selected crystallographic data for 2·CH2Cl2: C37H29AlCl2F15N3, monoclinic, space group P2(1)/c, a = 11.6507(7) Å, b = 16.8033(10) Å, c = 19.1096(12) Å, β = 94.747(3)°, V = 3728.3 (4) Å3, Z = 4, D calcd = 1.601 Mg/m3, GOF = 1.060, R 1 = 0.0512 [I >2σ(I)], wR2 = 0.1482. CCDC 972835 contains the supplementary crystallographic data for this structure.