Download PDF
Synthesis 2010(15): 2521-2526  
DOI: 10.1055/s-0029-1218831
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Enantiodivergent Formal Total Synthesis of Aspercyclide C from l-(+)-Tartaric Acid

Kavirayani R. Prasad*, Vasudeva Rao Gandi, John Eugene Nidhiry, Kavya S. Bhat
Department of Organic Chemistry, Indian Institute of Science, Bangalore 560 012, India
Fax: +91(80)23600529; e-Mail: prasad@orgchem.iisc.ernet.in;
Further Information

Publication History

Received 1 March 2010
Publication Date:
18 June 2010 (online)

    Permissions and Reprints All articles of this category

Abstract

The enantiodivergent formal syntheses of both enantio­mers of aspercyclide C is accomplished. Starting from l-(+)-tartaric acid, the key protected allylic alcohol, (3R,4R)-4-(methoxy­methoxy)non-1-en-3-ol is prepared, and is then elaborated into both enantiomers of 3-[(4-methoxybenzyl)oxy]non-1-en-4-ol via Mitsunobu­ inversion. Esterification with a known biaryl acid, followed by ring-closing metathesis and deprotection completes the syntheses.

Key words

aspercyclide C - total synthesis - tartaric acid - Mitsunobu inversion - ring-closing metathesis

    References

  • 1 Singh SB. Jayasuriya H. Zink DL. Polishook JD. Dombrowski AW. Zweerink H. Tetrahedron Lett.  2004,  45:  7605 
    CrossrefGoogle Scholar
  • 2a Pospsil J. Müller C. Fürstner A. Chem. Eur. J.  2009,  15:  5956 
    Google Scholar
  • 2b Fürstner A. Müller C. Chem. Commun.  2005,  5583 
    Google Scholar
  • 2c Carr JL. Offermann DA. Holdom MD. Dusart P. White AJP. Beavil AJ. Leatherbarrow RJ. Lindell SD. Sutton BJ. Spivey AC. Chem. Commun.  2010,  46:  1824 
    Google Scholar
  • 2d Ramana CV. Mondal MA. Puranik VG. Gurjar MK. Tetrahedron Lett.  2007,  48:  7524 
    Google Scholar
  • 3a Prasad KR. Gandi VR. Synlett  2009,  2593 
    Google Scholar
  • 3b Prasad KR. Gholap SL. J. Org. Chem.  2008,  73:  2 
    Google Scholar
  • 3c Prasad KR. Gholap SL. J. Org. Chem.  2008,  73:  2916 
    Google Scholar
  • 3d Prasad KR. Swain B. Tetrahedron: Asymmetry  2008,  19:  1134 
    Google Scholar
  • 3e Prasad KR. Gandi V. Tetrahedron: Asymmetry  2008,  19:  2616 
    Google Scholar
  • 3f Prasad KR. Chandrakumar A. J. Org. Chem.  2007,  72:  6312 
    Google Scholar
  • 3g Prasad KR. Dhaware M. Synthesis  2007,  3697 
    Google Scholar
  • 3h Prasad KR. Gholap SL. J. Org. Chem.  2006,  71:  3643 
    Google Scholar
  • 3i Prasad KR. Anbarasan P. Tetrahedron Lett.  2006,  47:  1433 
    Google Scholar
  • 3j Prasad KR. Anbarasan P. Tetrahedron: Asymmetry  2006,  17:  850 
    Google Scholar
  • 3k Prasad KR. Anbarasan P. Tetrahedron  2006,  62:  8303 
    Google Scholar
  • 3l Prasad KR. Anbarasan P. Synlett  2006,  2087 
    Google Scholar
  • 4 For an optimized synthesis of γ-hydroxy amides from tartaric acid amides, see: Prasad KR. Chandrakumar A. Tetrahedron  2007,  63:  1798 
    CrossrefGoogle Scholar
  • 5a Nugiel DA. Jakobs K. Worley T. Patel M. Kaltenbach RF. Meyer DT. Jadhav PK. De Lucca GV. Smyser TE. Klabe RM. Bacheler LT. Rayner MM. Seitz SP. J. Med. Chem.  1996,  39:  2156 
    Google Scholar
  • 5b McNulty J. Grunner V. Mao J. Tetrahedron Lett.  2001,  42:  5609 
    Google Scholar
  • 7a Swallen LC. Boord CE. J. Am. Chem. Soc.  1930,  52:  651 
    Google Scholar
  • For the application of this strategy in the synthesis of allylic alcohols, see:
  • 7b Schneider C. Kazmaier U. Synthesis  1998,  1314 
    Google Scholar
  • 7c Rama Rao AV. Reddy ER. Joshi BV. Yadav JS. Tetrahedron Lett.  1987,  28:  6497 
    Google Scholar
  • 8 Ghosh AK. Wang Y. Kim JT. J. Org. Chem.  2001,  66:  8973 
    CrossrefGoogle Scholar
  • 9 Mitsunobu O. Synthesis  1981,  1 
    Article in Thieme ConnectGoogle Scholar
6

Formation of the other diastereomer was not detected within the limits of ¹H NMR spectroscopy.

10

Biaryl acid 5 was prepared according to the method of Ramana et al., see ref. 2d.