Download PDF
Synthesis 2009(15): 2561-2569  
DOI: 10.1055/s-0029-1217390
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Enantioselective Synthesis of the 3C-Protease Inhibitor (-)-Thysanone by a Staunton-Weinreb Annulation Strategy

Jonathan Sperry, Tsz Ying Yuen, Margaret A. Brimble*
Department of Chemistry, University of Auckland, 23 Symonds Street, Auckland 1142, New Zealand
Fax: +64(9)3737422; e-Mail: m.brimble@auckland.ac.nz;
Further Information

Publication History

Received 27 February 2009
Publication Date:
08 June 2009 (online)

    Permissions and Reprints All articles of this category

Abstract

The total synthesis of (-)-thysanone is described. The key step involves the addition of an o-toluate anion to a lactone to create the naphthopyran framework (Staunton-Weinreb annulation). This synthesis further confirms the absolute stereochemistry of the natural product to be 1R,3S.

Key words

thysanone - Staunton-Weinreb annulation - total synthesis - natural products - polycycles

    References

  • 1 Callahan PL. Mizutani S. Colonno RJ. Proc. Natl. Acad. Sci. U.S.A.  1985,  82:  732 
    CrossrefGoogle Scholar
  • 2 Binford SL. Maldonado F. Brothers MA. Weady PT. Zalman LS. Meador JW. Matthews DA. Patick AK. Antimicrob. Agents Chemother.  2005,  49:  619 
    CrossrefGoogle Scholar
  • 3 Singh SB. Cordingley MG. Ball RG. Smith JL. Dombrowski AW. Goetz MA. Tetrahedron Lett.  1991,  32:  5279 
    CrossrefGoogle Scholar
  • 4 For a recent review on the isolation and synthesis of pyranonaphthoquinones, see: Sperry J. Bachu P. Brimble MA. Nat. Prod. Rep.  2008,  25:  376 
    CrossrefPubMedGoogle Scholar
  • 5 For a preliminary communication of this work, see: Sperry J. Brimble MA. Synlett  2008,  1910 
    Article in Thieme ConnectGoogle Scholar
  • For a previous 16-step total synthesis of (-)-thysanone, see:
  • 6a Gill M. Donner CD. Tetrahedron Lett.  1999,  40:  3921 
    Google Scholar
  • 6b Donner CD. Gill M. J. Chem. Soc., Perkin Trans. 1  2002,  938 
    Google Scholar
  • For analogue syntheses of thysanone, see:
  • 7a Brimble MA. Elliott RJR. McEwan JF. Aust. J. Chem.  2000,  53:  571 
    Google Scholar
  • 7b Brimble MA. Elliott RJR. Tetrahedron  2002,  58:  183 
    Google Scholar
  • 7c Kraus GA. Ogutu H. Tetrahedron  2002,  58:  7391 
    Google Scholar
  • 7d Bulbule VJ. Koranne PS. Deshpande VH. Borate HB. Tetrahedron  2007,  63:  166 
    Google Scholar
  • 7e Brimble MA. Houghton SI. Woodgate PD. Tetrahedron  2007,  63:  880 
    Google Scholar
  • 7f For a formal synthesis of thysanone, see: Bachu P. Sperry J. Brimble MA. Tetrahedron  2008,  64:  4827 
    Google Scholar
  • 7g Sawant RT. Waghmode SB. Tetrahedron  2009,  65:  1599 
    Google Scholar
  • 8a Hauser FM. Rhee RP. J. Org. Chem.  1978,  43:  178 
    Google Scholar
  • 8b Kraus GA. Sugimoto H. Tetrahedron Lett.  1978,  19:  2263 
    Google Scholar
  • For recent reviews on the Hauser-Kraus annulation, see:
  • 9a Rathwell K. Brimble MA. Synthesis  2007,  5:  643 
    Google Scholar
  • 9b Mal D. Pahari P. Chem. Rev.  2007,  107:  1892 
    Google Scholar
  • 10 Kuhn R. Kum K. Chem. Ber.  1962,  95:  2009 
    CrossrefGoogle Scholar
  • 11 Chiarello J. Jouillé MM. Tetrahedron  1988,  44:  41 
    CrossrefGoogle Scholar
  • 12 Drochner D. Hüttel W. Bode SE. Müller M. Karl U. Nieger M. Steglich W. Eur. J. Org. Chem.  2007,  1749 
    CrossrefGoogle Scholar
  • 13 Hauser FM. Rhee RP. Prassana S. Weinreb SM. Dodd JH. Synthesis  1980,  72 
    Article in Thieme ConnectGoogle Scholar
  • 14 Ramachandran PV. Reddy MVR. Brown HC. Tetrahedron Lett.  2000,  41:  583 
    CrossrefGoogle Scholar
  • 15 Shao L. Kawano H. Saburi M. Uchida Y. Tetrahedron  1993,  49:  1997 
    CrossrefGoogle Scholar
  • 16 A previous synthesis of (S)-semivioxanthin methyl ether has been reported. See: Deshpande VH. Rai B. Khan RA. Tetrahedron  1996,  52:  7159 
    CrossrefGoogle Scholar
  • 17a Evans GE. Leeper FJ. Murphy JA. Staunton J. J. Chem. Soc., Chem. Commun.  1979,  205 
    Google Scholar
  • 17b Dodd JH. Weinreb SM. Tetrahedron Lett.  1979,  38:  3593 
    Google Scholar
  • For some recent applications of this annulation in synthesis, see:
  • 17c Zhang Z. Yu B. J. Org. Chem.  2003,  68:  6309 
    Google Scholar
  • 17d Hill B. Rodrigo R. Org. Lett.  2005,  7:  5223 
    Google Scholar
  • 17e Bode SE. Drochner D. Müller M. Angew. Chem. Int. Ed.  2007,  46:  5916 
    Google Scholar
  • 17f Donner CD. Tetrahedron Lett.  2007,  48:  8888 
    Google Scholar
  • 17g Tan NPH. Donner CD. Tetrahedron Lett.  2008,  4160 
    Google Scholar
  • 18 Drochner D. Müller M. Eur. J. Org. Chem.  2001,  211 
    CrossrefGoogle Scholar
  • 19a Szántay C. Acta Chim. Hung.  1957,  12:  83 
    Google Scholar
  • 19b Banwell MG. Flynn BL. Stewart SG. J. Org. Chem.  1998,  63:  9139 
    Google Scholar