Download PDF
Synthesis 2012(8): 1258-1262  
DOI: 10.1055/s-0031-1289751
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Molybdenum-Mediated Deconjugation of α,β-Unsaturated Fused-Cyclopentenone Phosphonates

Dorit Moradova, Abraham Rubinsteina, Dmitri Gelman*b, Morris Srebnik†*a
a School of Pharmacy Institute for Drug Research, The Hebrew University of Jerusalem, P.O. Box 12065, Jerusalem 91120, Israel
Fax: +972(2)6585276; e-Mail: dgelman@chem.ch.huji.ac.il;
b Institute of Chemistry, The Hebrew University of Jerusalem, Edmund Safra Campus, 91904 Jerusalem, Israel
Further Information

Publication History

Received 9 January 2012
Publication Date:
16 March 2012 (online)

    Permissions and Reprints All articles of this category

Abstract

The synthesis of diethyl (3-alkyl-5-oxo-4,5,6,6a-tetra­hydro-1H-cyclopenta[c]furan-4-yl)phosphonates from the corresponding 3-allyloxy-1-propynylphosphonates is described. The in situ reaction involves two steps: an intramolecular Pauson-Khand reaction followed by an unusual double bond deconjugation mediated by molybdenum hexacarbonyl in dimethyl sulfoxide.

Key words

double bond isomerization - molybdenum - phosphonate - Pauson-Khand reaction - deconjugation

    References

  • 1 Quntar AA. Baum O. Reich R. Srebnik M. Arch. Pharm.  2004,  337:  76 
    Google Scholar
  • 2 Quntar AA. Gallily R. Katzavian G. Srebnik M. Eur. J. Pharmacol.  2007,  556:  9 
    Google Scholar
  • 3 Cristau HJ. Gazc MB. Mbianda XY. Geze A. Phosphorus, Sulfur Silicon Relat. Elem.  1996,  111:  759 
    Google Scholar
  • 4 Kiss T. Lazar I. Kafarski P. Met. Based Drugs  1994,  1:  247 
    Google Scholar
  • 5 Boduszek B. Phosphorus, Sulfur Silicon Relat. Elem.  1999,  146:  433 
    Google Scholar
  • 6 Farkas E. Katz Y. Bhusare S. Reich R. Röschenthaler GV. Königamann M. Breuer E. J. Biol. Inorg. Chem.  2004,  9:  307 
    Google Scholar
  • 7 Pergament I. Reich R. Srebnik M. Bioorg. Med. Chem. Lett.  2002,  12:  1215 
    Google Scholar
  • 8 Agamennone M. Campestre C. Preziuso S. Consalvi V. Crucianelli M. Mazza F. Politi V. Ragno R. Tortorella P. Gallina C. Eur. J. Med. Chem.  2005,  40:  271 
    Google Scholar
  • 9 Dembitsky VM. Quntar AA. Haj-Yehia A. Srebnik M. Mini Rev. Org. Chem.  2005,  2:  91 
    Google Scholar
  • 10 Baum O. Quntar AA. Demitsky VM. Srebnik M. Tetrahedron  2004,  60:  1359 
    Google Scholar
  • 11 Quntar AA. Baum O. Shibli A. Dembitsky VM. Srebnik M. Angew. Chem. Int. Ed.  2003,  42:  4777 
    Google Scholar
  • 12 Quntar AA. Melman A. Srebnik M. J. Org. Chem.  2002,  67:  3769 
    Google Scholar
  • 13 Quntar AA. Dembitsky VM. Srebnik M. Org. Lett.  2003,  5:  357 
    Google Scholar
  • 14 Ben-Valid S. Quntar AA. Srebnik M. J. Org. Chem.  2005,  70:  3554 
    Google Scholar
  • 15 Quntar AA. Srebnik M. Org. Lett.  2001,  3:  1379 
    Google Scholar
  • 16 Quntar AA. Srebnik M. Chem. Commun.  2003,  58 
    Google Scholar
  • 17 Quntar AA. Srebnik M. J. Org. Chem.  2006,  71:  730 
    Google Scholar
  • 18 Quntar AA. Melman A. Srebnik M. Synlett  2002,  61 
    Google Scholar
  • 19 Quntar AA. Rosenthal D. Srebnik M. Tetrahedron  2006,  62:  5995 
    Google Scholar
  • 20 Sinelnikove Y. Rubinstein A. Srebnik M. Quntar AA. Tetrahedron Lett.  2009,  50:  867 
    Google Scholar
  • 21 Moradov D. Quntar AA. Youssef M. Smoum R. Rubinstein A. Srebnik M. J. Org. Chem.  2009,  74:  1029 
    Google Scholar
  • 22 For an excellent review on alternative synthetic approaches toward this class of compounds, see: Ananikov VP. Khemchyan LL. Beletskaya IP. Synlett  2009,  2375 
    Google Scholar
  • 23 Gerber JP. Modro TA. Wagener CCP. Zwierzak A. Heteroat. Chem.  1991,  2:  643 
    Google Scholar
  • 24 Kiddle JJ. Babler JH. J. Org. Chem.  1993,  58:  3572 
    Google Scholar
  • 25 Modro AM. Modro TA. Can. J. Chem.  1988,  66:  1541 
    Google Scholar
  • 26 Luo FT. Hsieh LC. Tetrahedron Lett.  1994,  35:  9585 
    Google Scholar
  • 27 Oh JH. Ahn BS. Han JS. Lee SD. Kim SW. Lee H. Bull. Korean Chem. Soc.  2008,  29:  2202 
    Google Scholar
  • 28 Terada M. Yoda Y. J. Am. Chem. Soc.  2009,  131:  6354 
    Google Scholar
  • 29 Sharma SK. Srivastava VK. Padya PH. Jasra RV. Catal. Commun.  2005,  6:  205 
    Google Scholar
  • 30 Sharma SK. Srivastava VK. Jasra RV. J. Mol. Catal. A: Chem.  2006,  245:  200 
    Google Scholar
  • 31 Wilm M. Mann M. Anal. Chem.  1996,  68:  1 
    Google Scholar
32

Different sets of reaction conditions were examined during the optimization studies. We observed that after the formation of intermediate 2, from 1, using two equivalents of Mo(CO)6 and 10 equivalents of DMSO in toluene at 100 ˚C for one hour, the presence of toluene slowed down the rate of conversion of 2 into 3. Hence, toluene was evaporated at this stage.