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Synthesis 2010(9): 1536-1542  
DOI: 10.1055/s-0029-1218704
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Exceptionally Easy Ring Cleavage of Benzimidazoles by α,β-Acetylenic γ-Hydroxy Nitriles and Water

Boris A. Trofimov*, Ludmila V. Andriyankova, Lina P. Nikitina, Kseniya V. Belyaeva, Anastasiya G. Mal’kina, Andrei V. Afonin
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russian Federation
Fax: +7(3952)419346; e-Mail: boris_trofimov@irioch.irk.ru;
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Publication History

Received 27 January 2010
Publication Date:
15 March 2010 (online)

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Abstract

The three-component reaction of a benzimidazole with an α,β-acetylenic γ-hydroxy nitrile and water in acetonitrile at 20-25 ˚C for seven days or at 45-50 ˚C for six hours results in cleavage of the imidazole ring to afford the corresponding (2-{[(3E)-5-aminofuran-3(2H)-ylidene]amino}phenyl)formamide exclusively in 84-99% yield. The synthesis involves multipositional cascade transformations of the intermediate hemiaminals formed from the primary zwitterions and water.

Key words

alkynes - benzimidazoles - heterocycles - multicomponent reactions - nitriles - ring opening - polycycles

    References

  • 1 Heaney H. Ahn JS. In Comprehensive Heterocyclic Chemistry II   Vol. 2:  Katritzky AR. Rees RFV. Pergamon; Oxford: 1996.  p.297-436  
    Google Scholar
  • 2 Maier M. In Organic Synthesis Highlights II   Waldman H. VCH; Weinheim: 1995.  p.231-242  
    Google Scholar
  • 3a Ortega MJ. Zubia E. Ocana JM. Naranjo S. Salva J. Tetrahedron  2000,  56:  3963 
    Google Scholar
  • 3b Bellina F. Anselmi C. Viel S. Mannina L. Rossi R. Tetrahedron  2001,  57:  9997 
    Google Scholar
  • 3c Bellina F. Anselmi C. Rossi R. Tetrahedron Lett.  2002,  43:  2023 
    Google Scholar
  • 3d Bellina F. Anselmi C. Martina F. Rossi R. Eur. J. Org. Chem.  2003,  2290 
    Google Scholar
  • 4a Yang X. Shimizu Y. Steiner JR. Clardy J. Tetrahedron Lett.  1993,  34:  761 
    Google Scholar
  • 4b Bellina F. Rossi R. Synthesis  2002,  2729 
    Google Scholar
  • 5 Bellina F. Falchi E. Rossi R. Tetrahedron  2003,  59:  9091 
    CrossrefGoogle Scholar
  • 6 Liu Y. Song F. Song Zh. Liu M. Yan B. Org. Lett.  2005,  7:  5409 
    Google Scholar
  • 7a Roggo BE. Petersen F. Delmendo R. Jenny HB. Peter HH. Roesel J. J. Antibiot.  1994,  47:  136 
    Google Scholar
  • 7b Effenberger F. Syed J. Tetrahedron: Asymmetry  1998,  9:  817 
    Google Scholar
  • 7c Van Quaquebeke E. Simon G. André A. Dewelle J. Yazidi M. Bruyneel F. Tuti J. Nacoulma O. Guissou P. Decaestecker C. Braekman J.-C. Kiss R. Darro F. J. Med. Chem.  2005,  48:  849 
    Google Scholar
  • 7d Bousserouel H. Litaudon M. Morleo B. Martin M.-T. Thoison O. Nosjean O. Boutin JA. Renard P. Sévenet T. Tetrahedron  2005,  61:  845 
    Google Scholar
  • 7e Dai S.-J. Tao J.-Y. Liu K. Jiang Y.-T. Shen L. Phytochemistry  2006,  67:  1326 
    Google Scholar
  • 7f Zografos AL. Georgiadis D. Synthesis  2006,  3157 
    Google Scholar
  • 8 Tahir H. Hindsgaul O. J. Org. Chem.  2000,  65:  911 
    CrossrefGoogle Scholar
  • 9 Shin SS. Byun Y. Lim KM. Choi JK. Lee K.-W. Moh JH. Kim JK. Jeong YS. Kim JY. Choi YH. Koh H.-J. Park Y.-H. Oh YI. Noh M.-S. Chung S.
    J. Med. Chem.  2004,  47:  792 
    CrossrefPubMedGoogle Scholar
  • 10 Grossmann G. Jolivet B. Bornand M. Séquin U. Spindler K.-D. Synthesis  2005,  1543 
    Article in Thieme ConnectGoogle Scholar
  • 11 Trofimov BA. Andriyankova LV. Mal’kina AG. Belyaeva KV. Nikitina LP. Dyachenko OA. Kazheva ON. Chekhlov AN. Shilov GV. Afonin AV. Ushakov IA. Baikalova LV. Eur. J. Org. Chem.  2007,  1018 
    CrossrefGoogle Scholar
  • 12a Landor SR. Demetriou B. Grzeskowiak R. Pavey D. J. Organomet. Chem.  1975,  93:  129 
    Google Scholar
  • 12b Hopf H. Witulski B. In Modern Acetylene Chemistry   Stang PJ. Diederich F. VCH; Weinheim: 1995.  p.33-67  
    Google Scholar
  • 12c Trofimov BA. Mal’kina AG. Heterocycles  1999,  51:  2485 
    Google Scholar
  • 12d Trofimov BA. Andriyankova LV. Shaikhudinova SI. Kazantseva TI. Mal’kina AG. Zhivet’ev SA. Afonin AV. Synthesis  2002,  853 
    Google Scholar
  • 13 Starikova OV. Dolgushin GV. Larina LI. Komarova TN. Lopyrev VA. ARKIVOC  2003,  (xiii):  119 
    Google Scholar