Download PDF
Synlett 2004(8): 1437-1439  
DOI: 10.1055/s-2004-825624
LETTER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Membranacin

Geoffrey D. Heada, William G. Whittinghamb, Richard C. D. Brown*a
a School of Chemistry, University of Southampton, Highfield, Southampton S017 1BJ, UK
Fax: +44(23)80596805; e-Mail: rcb1@soton.ac.uk;
b Syngenta, Jealott’s Hill International Research Centre, Bracknell RG42 6EY, UK
Further Information

Publication History

Received 17 March 2004
Publication Date:
08 June 2004 (online)

    Permissions and Reprints All articles of this category

Abstract

The synthesis of the Annonaceous acetogenin membranacin (2) has been achieved, using transition metal-oxo and ­transition metal-peroxy species in the key steps.

Key words

oxidations - asymmetric synthesis - natural products - manganese - total synthesis

    References

  • For recent reviews:
  • 1a Zafra-Polo MC. Figadère B. Gallardo T. Tormo JR. Cortes D. Phytochemistry  1998,  48:  1087 
    CrossrefGoogle Scholar
  • 1b Alali FQ. Liu XX. McLaughlin JL. J. Nat. Prod.  1999,  62:  504 
    CrossrefGoogle Scholar
  • For reviews of acetogenin synthesis see ref. 1 and:
  • 2a Hoppe R. Scharf HD. Synthesis  1995,  1447 
    Google Scholar
  • 2b Figadère B. Cavé A. In Studies in Natural Products Chemistry   Vol. 18:  Rahman AU. Elsevier Science; Amsterdam: 1996.  p.193-227  
    Google Scholar
  • 2c Marshall JA. Hinkle KW. Hagedorn CE. Isr. J. Chem.  1997,  37:  97 
    Google Scholar
  • 2d Casiraghi G. Zanardi F. Battistini L. Rassu G. Appendino G. Chemtracts  1998,  11:  803 
    Google Scholar
  • For selected recent approaches to the synthesis of acetogenins:
  • 3a Baurle S. Hoppen S. Koert U. Angew. Chem. Int. Ed.  1999,  38:  1263 
    CrossrefGoogle Scholar
  • 3b Marshall JA. Piettre A. Paige MA. Valeriote F. J. Org. Chem.  2003,  68:  1771 
    CrossrefGoogle Scholar
  • 3c Sinha SC. Sinha A. Sinha SC. Keinan E. J. Am. Chem. Soc.  1998,  120:  4017 
    CrossrefGoogle Scholar
  • 3d Trost BM. Calkins TL. Bochet CG. Angew. Chem., Int. Ed. Engl.  1997,  36:  2632 
    CrossrefGoogle Scholar
  • 3e Hanessian S. Grillo TA. J. Org. Chem.  1998,  63:  1049 
    CrossrefGoogle Scholar
  • 3f Kuriyama W. Ishigami K. Kitahara T. Heterocycles  1999,  50:  981 
    CrossrefGoogle Scholar
  • 3g Yu Q. Wu YK. Ding H. Wu YL. J. Chem. Soc., Perkin Trans. 1  1999,  1183 
    CrossrefGoogle Scholar
  • 3h Ruan ZM. Dabideen D. Blumenstein M. Mootoo DR. Tetrahedron  2000,  56:  9203 
    CrossrefGoogle Scholar
  • 3i Zanardi F. Battistini L. Rassu G. Auzzas L. Pinna L. Marzocchi L. Acquotti D. Casiraghi G. J. Org. Chem.  2000,  65:  2048 
    CrossrefGoogle Scholar
  • 3j Hu TS. Yu Q. Wu YL. Wu YK. J. Org. Chem.  2001,  66:  853 
    CrossrefGoogle Scholar
  • 3k Dixon DJ. Ley SV. Reynolds DJ. Chem.-Eur. J.  2002,  8:  1621 
    CrossrefGoogle Scholar
  • 3l Cecil ARL. Brown RCD. Org. Lett.  2002,  4:  3715 
    CrossrefGoogle Scholar
  • 4 Brown RCD. Hughes RM. Keily J. Kenney A. Chem. Commun.  2000,  1735 
    CrossrefGoogle Scholar
  • 5a Saez J. Sahpaz S. Villaescusa L. Hocquemiller R. Cave A. Cortes D. J. Nat. Prod.  1993,  56:  351 
    CrossrefGoogle Scholar
  • 5b Gonzalez MC. Lavaud C. Gallardo T. Zafra-Polo MC. Cortes D. Tetrahedron  1998,  54:  6079 
    CrossrefGoogle Scholar
  • For examples of the oxidative cyclisation of 1,5-dienes using metal-oxo species see ref. 3 and:
  • 6a (MnO4 -): Klein E. Rojahn W. Tetrahedron  1979,  21:  2353 
    Google Scholar
  • 6b Walba DM. Przybyla CA. Walker CBJ. J. Am. Chem. Soc.  1990,  112:  5624 
    Google Scholar
  • 6c Kocienski PJ. Brown RCD. Pommier A. Procter M. Schmidt B. J. Chem. Soc., Perkin Trans. 1  1998,  9 
    Google Scholar
  • 6d Ruthenium: Carlsen PHJ. Katsuki T. Martin VS. Sharpless KB. J. Org. Chem.  1981,  46:  3936 
    Google Scholar
  • 6e Albarella L. Musumeci D. Sica D. Eur. J. Org. Chem.  2001,  997 
    Google Scholar
  • 6f Bifulco G. Caserta T. Gomez-Paloma L. Piccialli V. Tetrahedron Lett.  2003,  44:  3429 
    Google Scholar
  • 6g OsO4: de Champdore M. Lasalvia M. Piccialli V. Tetrahedron Lett.  1998,  39:  9781 
    Google Scholar
  • 6h Donohoe TJ. Butterworth S. Angew. Chem. Int. Ed.  2003,  42:  978 
    Google Scholar
  • 7 Brown RCD. Bataille CJ. Hughes RM. Kenney A. Luker TJ. J. Org. Chem.  2002,  67:  8079 
    CrossrefGoogle Scholar
  • 9 Saito S. Ishikawa T. Kuroda A. Koga K. Moriwake T. Tetrahedron  1992,  48:  4067 
    CrossrefGoogle Scholar
  • 10 Hoye TR. Tan L. Tetrahedron Lett.  1995,  36:  1981 
    CrossrefGoogle Scholar
  • 11 Trost BM. Müller TJJ. Martinez J. J. Am. Chem. Soc.  1995,  117:  1888 
    CrossrefGoogle Scholar
8

A single diastereoisomer 3 was isolated from the reaction mixture, although oxidative cyclisation of similar substrates has been found to proceed with a diastereoselectivity of approximately 6:1.