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Synlett 2010(18): 2721-2724  
DOI: 10.1055/s-0030-1259010
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Formal Synthesis of AB3217-A from Anisomycin Using a Directed Benzylic Oxidation

Julie Touega, Christopher R. A. Godfrey*a, Jane E. Wibleyb
a Syngenta Crop Protection Münchwilen AG, WST-820.1.15, Schaffhauserstrasse, 4332 Stein, Switzerland
e-Mail: chris.godfrey@syngenta.com;
b Syngenta Crop Protection Jealott’s Hill International Research Centre, Bracknell, Berkshire, R42 6EY, UK
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Publikationsverlauf

Received 9 September 2010
Publikationsdatum:
22. Oktober 2010 (online)

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Abstract

A formal synthesis of the insecticidal natural product AB3217-A involving an unusual diastereoselective benzylic oxidation is described.

Key words

natural product - anisomycin - AB3217-A - benzylic oxidation - insecticide

    References and Notes

  • 1a Kanbe K. Mimura Y. Tamamura T. Yatagai S. Sato Y. Takahashi A. Sato S. J. Antibiot.  1992,  45:  548 
    Suche in Google Scholar
  • 1b Kanbe K. Takahashi A. Tamamura T. Sato K. Naganawa H. Takeuchi T. J. Antibiot.  1992,  45:  568 
    Suche in Google Scholar
  • 1c Kim W.-G. Kim J.-P. Park D.-J. Kim Ch.-J. Kwak SS. Yoo I.-D. Agric. Chem. Biotech.  1996,  39:  153 
    Suche in Google Scholar
  • 2a Nakata M. Tamai T. Kamio T. Kinoshita M. Tatsuta K. Bull. Chem. Soc. Jpn.  1994,  67:  3057 
    Suche in Google Scholar
  • 2b Nakata M. Tamai T. Kamio T. Kinoshita M. Tatsuta K. Tetrahedron Lett.  1994,  35:  3099 
    Suche in Google Scholar
  • 3 Hungerbuehler E. Seebach D. Helv. Chim. Acta  1981,  64:  687 
    CrossrefSuche in Google Scholar
  • 4a Beereboom JJ. Butler K. Pennington E.-C. J. Org. Chem.  1965,  30:  2334 
    Suche in Google Scholar
  • 4b Butler K. J. Org. Chem.  1966,  31:  317 
    Suche in Google Scholar
  • 4c Sobin BA. Tanner FW. J. Am. Chem. Soc.  1954,  76:  4053 
    Suche in Google Scholar
  • 4d Macias-Silva M. Vazquez-Victorio G. Hernandez-Damian J. Curr. Chem. Biol.  2010,  4:  124 
    Suche in Google Scholar
  • 5a Shimamoto K. Ohfune Y. Tetrahedron Lett.  1988,  29:  5177 
    Suche in Google Scholar
  • 5b For a recent example see: Bulman Page PC. Buckley BR. Rassias GA. Blacker AJ. Eur. J. Org. Chem.  2006,  803 
  • For precedents for trans intramolecular acetyl migration, see:
  • 6a Deng S. Chang C.-WT. Synlett  2006,  756 
  • 6b Markad SD. Schmidt RR. Eur. J. Org. Chem.  2009,  5002 
  • For a recent example of benzylation using phenyl diazo-methane, see:
  • 8a Dake G. Fenster MDB. Hurley PB. Patrick BO. J. Org. Chem.  2004,  69:  5668 
    Suche in Google Scholar
  • For procedures using benzyl triflate, see:
  • 8b Berry JM. Hall LD. Carbohydr. Res.  1976,  47:  307 
    Suche in Google Scholar
  • 8c Fleming I. Leslie CP. J. Chem. Soc., Perkin Trans. 1  1996,  1197 
  • 9 Haddad M. Imogaï H. Larchevêque M. J. Org. Chem.  1998,  63:  5680 
    CrossrefSuche in Google Scholar
7

The hypothesis that the migration of the acetate proceeds via formation of an epoxide was ruled out. If an epoxide was formed and re-opened by the acetate, the stereochemistry of the two hydroxy groups on the pyrrolidine moiety would be inverted, which is not the case as can be observed on the crystal structure of 6 (Figure  [³] ).