Download PDF
Synthesis 2011(7): 1067-1070  
DOI: 10.1055/s-0030-1258451
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

An Enantiospecific Route to (+)-(1R,3S)-cis-Chrysanthemic Acid from (-)-d-Pantolactone [¹]

Atul K. Hajarea,b, Laxmikant S. Datrangea, Y. L. N. Murthyb, Debnath Bhuniyaa, D. Srinivasa Reddy*a,c
a Discovery Chemistry, Advinus Therapeutics Ltd., Quantum Towers, Plot No. 9, Rajiv Gandhi Infotech Park, Phase-I, Hinjewadi, Pune 411057, India
b Department of Organic Chemistry, Andhra University, Visakhapatnam 530003, India
c Present address: , National Chemical Laboratory (CSIR, India), Division of Organic Chemistry, Dr. Homi Bhabha Road, Pune 411008, Maharashtra, India
Fax: +91(20)66539620; e-Mail: ds.reddy@ncl.res.in; e-Mail: dsreddy88@yahoo.com;
Further Information

Publication History

Received 3 December 2010
Publication Date:
01 March 2011 (online)

    Permissions and Reprints All articles of this category

Abstract

In this paper, a novel route for the synthesis of (+)-(1R,3S)-cis-chrysanthemic acid is described. The use of readily available (-)-d-pantolactone as a starting point, application of ring-closing metathesis to form the cyclopentene intermediate, and Haller-Bauer/Grob-type fragmentation to form the target compound are the highlights of the present synthesis.

Key words

ring closure - stereoselective synthesis - Wittig reaction - alkenes - metathesis

1

Advinus Publication No.: ADV-A-010.

    References

  • 2a Itagaki M. Suenobu K. Org. Process Res. Dev.  2007,  11:  509 
    Search in Google Scholar
  • 2b Jeanmart S. Aust. J. Chem.  2003,  56:  559 
    Search in Google Scholar
  • 2c Fishman A. Kellner D. Ioffe D. Shapiro E. Org. Process Res. Dev.  2000,  4:  77 
    Search in Google Scholar
  • 2d Naumann K. Chemistry of Plant Protection, Synthetic Pyrethroid Insecticides   Vol. 5:  Springer; Berlin: 1990. and references cited therein
    Search in Google Scholar
  • Selected references for previous syntheses:
  • 3a Krief A. Jeanmart S. Kremer A. J. Org. Chem.  2008,  73:  9795 
    Search in Google Scholar
  • 3b Krief A. Gondal HY. Kremer A. Chem. Commun.  2008,  4753 
  • 3c Krief A. Kremer A. Synlett  2007,  607 
  • 3d Krief A. Swinnen D. Tetrahedron Lett.  1996,  37:  7123 
    Search in Google Scholar
  • 3e Krief A. Surleraux D. Ropson N. Tetrahedron: Asymmetry  1993,  4:  289 
    Search in Google Scholar
  • 3f Lambs L. Singh NP. Biellmann JF. J. Org. Chem.  1992,  57:  6301 
    Search in Google Scholar
  • 3g Krief A. Surleraux D. Robson MJ. Synlett  1991,  276 
  • 3h Krief A. Surleraux D. Frauenrath H. Tetrahedron Lett.  1988,  29:  6157 
    Search in Google Scholar
  • 3i Mulhr J. Kappert M. Angew. Chem., Int. Ed. Engl.  1983,  22:  63 
    Search in Google Scholar
  • 3j Sobti R. Dev S. Tetrahedron  1974,  30:  2927 
    Search in Google Scholar
  • 3k Krief A. Kremer A. Tetrahedron Lett.  2010,  51:  304 
    Search in Google Scholar
  • See earlier references from this group which use the pantolactone chiral pool approach:
  • 4a Hajare A. Datrange L. Vyas S. Bhuniya D. Reddy DS. Tetrahedron Lett.  2010,  51:  5291 
    Search in Google Scholar
  • 4b Reddy DS. Srinivas G. Rajesh BM. Kannan M. Rajale TV. Iqbal J. Tetrahedron Lett.  2006,  47:  6373 
    Search in Google Scholar
  • 4c Hajare A. Ravikumar V. Khaleel S. Bhuniya D. Reddy DS. J. Org. Chem.  2011,  76:  963 
    Search in Google Scholar
  • 5a Tombo GMR. Bellus D. Angew. Chem., Int. Ed. Engl.  1991,  30:  1193 
    Search in Google Scholar
  • 5b Elliott M. Pestic. Sci.  1989,  27:  337 
    Search in Google Scholar
  • 5c Ackermann P. Bourgeois F. Drabek J. Pestic. Sci.  1980,  11:  169 
    Search in Google Scholar
  • 6a Akbutina FA. Sandretdinov IF. Selezneva NK. Miftakhov MS. Mendeleev Commun.  2003,  3:  151 
    Search in Google Scholar
  • 6b Pirrung FOH. Hiemstra H. Speckamp WN. Kaptein B. Schoemaker HE. Synthesis  1995,  458 
  • 7 Previously, the same alcohol was prepared from (-)-panto-lactone in 10 steps with an overall yield of ˜34% using an alternate route. Miyaoka H. Sagawa S. Nagaoka H. Yamada Y. Tetrahedron: Asymmetry  1995,  6:  587 
    CrossrefSearch in Google Scholar
  • 8 Isopropyldiphenylsulfonium tetrafluoroborate was synthesized according to the general procedure reported in the literature: Matsuyama H. Nakamura T. Iyoda M. J. Org. Chem.  2000,  65:  4796 
    CrossrefSearch in Google Scholar
  • 9 Dauvergne J. Happe AM. Jadhav V. Justice D. Matos M.-C. McCormack PJ. Pitts MR. Roberts SM. Singh SK. Snape TJ. Whittall J. Tetrahedron  2004,  60:  2559 
    CrossrefSearch in Google Scholar
1

Advinus Publication No.: ADV-A-010.