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Synthesis 2010(14): 2419-2423  
DOI: 10.1055/s-0029-1218784
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of (±)-Diospongin A: A Hetero-Diels-Alder and C-Glycosylation Approach

Jesse D. More*
Department of Chemistry, Loyola University Maryland, 4501 North Charles Street, Baltimore, MD 21210, USA
Fax: +1(410)6172803; e-Mail: jdmore@loyola.edu;
Further Information

Publication History

Received 21 January 2010
Publication Date:
10 May 2010 (online)

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Abstract

The racemic natural product diospongin A has been prepared using a short and stereoselective sequence. Key steps include a hetero-Diels-Alder reaction and an anchimeric assistance-controlled C-glycosylation

Key words

Diels-Alder reaction - glycosylation - neighboring-group effects - natural products

    References

  • 1 Yin J. Kouda K. Tezuka Y. Tran Q.-L. Miyahara T. Chen Y. Kadota S. Planta Med.  2004,  70:  54 
    Article in Thieme ConnectPubMedGoogle Scholar
  • 2a Bressy B. Allais F. Cossy J. Synlett  2006,  3455 
    Google Scholar
  • 2b Bates RW. Song P. Tetrahedron  2007,  63:  4497 
    Google Scholar
  • 2c Sabitha G. Padmaja P. Yadav JS. Helv. Chim. Acta  2008,  91:  2235 
    Google Scholar
  • 2d Yadav JS. Padmavani B. Reddy BVS. Venugopal Ch. Rao AB. Synlett  2007,  2045 
    Google Scholar
  • 2e Hiebel M.-A. Pelotier B. Piva O. Tetrahedron  2007,  63:  7874 
    Google Scholar
  • 2f Lee K. Kim H. Hong J. Org. Lett.  2009,  11:  5202 
    Google Scholar
  • 2g Kawai N. Hande SM. Uenishi J. Tetrahedron  2007,  63:  9049 
    Google Scholar
  • 2h Wang H. Shuhler BJ. Xian M. Synlett  2008,  2651 
    Google Scholar
  • 2i Sawant KB. Jennings MP.
    J. Org. Chem.  2006,  71:  7911 
    Google Scholar
  • 3 While this manuscript was in preparation, a hetero-Diels-Alder approach to the diospongins was reported, see: Kumaraswamy G. Ramakrishna G. Naresh P. Jagadeesh B. Sridhar B. J. Org. Chem.  2009,  74:  8468 
    CrossrefPubMedGoogle Scholar
  • For general reviews of neighboring-group participation in glycosylation, see:
  • 4a Demchenko A. In Handbook of Chemical Glycosylation   Demchenko A. Wiley-VCH; Weinheim: 2008.  p.5-6  
    Google Scholar
  • 4b Hunig S. Angew. Chem., Int. Ed. Engl.  1964,  3:  548 
    Google Scholar
  • 5 Danishefsky S. Kerwin JF. Kobayashi S. J. Am. Chem. Soc.  1982,  104:  358 
    CrossrefGoogle Scholar
  • 6 For a review, see: Pellissier H. Tetrahedron  2009,  65:  2839 
    CrossrefGoogle Scholar
  • 8 Ayala L. Lucero CG. Romero JAC. Tabacco SA. Woerpel KA. J. Am. Chem. Soc.  2003,  125:  15521 
    CrossrefPubMedGoogle Scholar
  • For examples of 1,3-stereocontrol in O-glycosylation via anchimeric assistance, see:
  • 9a Wiesner K. Tsai TYR. Jin H. Helv. Chim. Acta  1985,  68:  300 
    Google Scholar
  • 9b Binkley RW. Koholic DJ. J. Carbohydr. Chem.  1988,  7:  487 
    Google Scholar
  • 9c Tanaka H. Yoshizawa A. Takahashi T. Angew. Chem. Int. Ed.  2007,  46:  2505 
    Google Scholar
  • For reviews of 2-deoxyglycoside synthesis, see:
  • 9d Hou D. Lowary TL. Carbohydr. Res.  2009,  344:  1911 
    Google Scholar
  • 9e Marzabadi C. Franck RW. Tetrahedron  2000,  56:  8385 
    Google Scholar
  • 10a Joly GD. Jacobsen EN. Org. Lett.  2002,  4:  1795 
    Google Scholar
  • 10b Joly GD. Ph.D. Thesis   Harvard University; Cambridge USA: 2004. 
    Google Scholar
  • 11a Moilanen SB. Tan DS. Org. Biomol. Chem.  2005,  3:  798 
    Google Scholar
  • 11b Kaneno D. Tomoda S. Tetrahedron Lett.  2009,  50:  329 
    Google Scholar
  • 12 For a review, see: Corey EJ. Helal CJ. Angew. Chem. Int. Ed.  1998,  37:  1986 
    CrossrefPubMedGoogle Scholar
  • 13 Gemal AL. Luche JL. J. Am. Chem. Soc.  1981,  103:  5454 
    CrossrefGoogle Scholar
  • 14 Berkowitz DB. Danishefsky SJ. Schulte GK. J. Am. Chem. Soc.  1992,  114:  4518 
    CrossrefGoogle Scholar
  • 15 Mitsunobu O. Synthesis  1980,  1 
    Article in Thieme ConnectGoogle Scholar
  • 16 For a review, see: Ferrier RJ. Top. Curr. Chem.  2001,  215:  153 
    Google Scholar
  • 17 Bolitt V. Mioskowski C. Lee S.-G. Falck JR. J. Org. Chem.  1990,  55:  5812 
    CrossrefGoogle Scholar
  • 18 Reaction at lower temperatures gave little or no conversion, which is congruous with sluggish SN2 displacement of an equatorial leaving group. In the case of 11, a ring-flip to give an axial leaving group would force the phenyl group into a disfavored axial position. See: Eliel EL. Wilen SH. Mander LN. In Stereochemistry of Organic Compounds   John Wiley and Sons; New York: 1994.  p.723 
    Google Scholar
7

Sawant and Jennings also synthesized 1 by reduction of an analogous oxocarbenium ion. See ref. 2i.