Download PDF
Synthesis 2010(21): 3649-3656  
DOI: 10.1055/s-0030-1258227
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Trapping the π-Allylpalladium Intermediate from Fulvene-Derived Azabicyclic Olefin with Soft Nucleophiles

Rani Rajan, Jubi John, Sreeja Thulasi, Nayana Joseph, K. V. Radhakrishnan*, R. C. Sawant
Organic Chemistry Section of Chemical Sciences and Technology Division, National Institute for Interdisciplinary Science and Technology (NIIST)-CSIR, Trivandrum 695 019, India
Fax: +91(471)2491712; e-Mail: radhupreethi@rediffmail.com;
Further Information

Publication History

Received 17 June 2010
Publication Date:
25 August 2010 (online)

    Permissions and Reprints All articles of this category

Abstract

A facile method for the synthesis of a new class of disubstituted alkylidenecyclopentenes has been introduced. The methodology involves the palladium-catalyzed ring opening of pentafulvene-derived bicyclic hydrazines with phenols and active methylene compounds, furnishing 1,4-disubstituted alkylidenecyclopentenes in good yield. The utility of multiple points of functionalization was effectively demonstrated by the synthesis of a substituted cyclopentanone and 2-hydrazinofulvene.

Key words

azabicyclic olefin - palladium - soft nucleophile - alkylidenecyclopentene - substituted cyclopentanone - 2-hydrazinofulvene

    References

  • 1 Hudlicky T. Price JD. Chem. Rev.  1989,  89:  1467 
    CrossrefGoogle Scholar
  • 2a Storsberg J. Nandakumar MV. Sankaranarayanan S. Kaufmann DE. Adv. Synth. Catal.  2001,  343:  177 
    Google Scholar
  • 2b Yao M.-L. Adiwidjaja G. Kaufmann DE. Angew. Chem. Int. Ed.  2002,  41:  3375 
    Google Scholar
  • 2c Pineschi M. Moro FD. Crotti P. Macchia F. Org. Lett.  2005,  7:  3605 
    Google Scholar
  • 2d Bournaud C. Falciola C. Lecourt T. Rosset S. Alexakis A. Micouin L. Org. Lett.  2006,  8:  3581 
    Google Scholar
  • 2e Radhakrishnan KV. Sajisha VS. Anas S. Krishnan KS. Synlett  2005,  2273 
    Google Scholar
  • 2f Sajisha VS. Mohanlal S. Anas S. Radhakrishnan KV. Tetrahedron  2006,  62:  3997 
    Google Scholar
  • 2g Sajisha VS. Radhakrishnan KV. Adv. Synth. Catal.  2006,  348:  924 
    Google Scholar
  • 2h John J. Adarsh B. Radhakrishnan KV. Tetrahedron  2010,  66:  1383 
    Google Scholar
  • 3 Bian J. Wingerden MV. Ready JM. J. Am. Chem. Soc.  2006,  128:  7428 
    Google Scholar
  • 4 Brady SF. Singh MP. Janso J. Clardy J. J. Am. Chem. Soc.  2000,  122:  2116 
    CrossrefGoogle Scholar
  • 5 Trost BM. Dong L. Schroeder GM. J. Am. Chem. Soc.  2005,  127:  10259 
    Google Scholar
  • 6a Trost BM. Chan DMT. J. Am. Chem. Soc.  1979,  101:  6429 
    Google Scholar
  • 6b Trost BM. Chan DMT. J. Am. Chem. Soc.  1979,  101:  6432 
    Google Scholar
  • 7a Yamamoto Y. Ohkoshi N. Kameda M. Itoh K. J. Org. Chem.  1999,  64:  2178 
    Google Scholar
  • 7b Binder JT. Crone B. Haug TT. Menz H. Kirsch SF. Org. Lett.  2008,  10:  1025 
    Google Scholar
  • 7c Oestreich M. Frohlich R. Hoppe D. J. Org. Chem.  1999,  64:  8616 
    Google Scholar
  • 7d Marco-Contelles J. Rodriguez M. Tetrahedron Lett.  1998,  39:  6749 
    Google Scholar
  • 7e Ballini R. Bosica G. Florini D. Victoria M. Petrini M. Org. Lett.  2001,  3:  1265 
    Google Scholar
  • 8 Hayashi M. Ohmatsu T. Meng YP. Saigo K. Angew Chem. Int. Ed.  1998,  37:  837 
    CrossrefGoogle Scholar
  • 9 Corkey BK. Toste FD. J. Am. Chem. Soc.  2005,  127:  17168 
    CrossrefGoogle Scholar
  • 10a Barluenga J. Vicente R. Barrio P. Lopez LA. Tomas M. J. Am. Chem. Soc.  2004,  126:  5974 
    Google Scholar
  • 10b Barluenga J. Vicente R. Barrio P. Lopez LA. Tomas M. J. Am. Chem. Soc.  2006,  128:  7050 
    Google Scholar
  • 11 Tang X.-Y. Shi M. J. Org. Chem.  2010,  75:  902 
    CrossrefGoogle Scholar
  • 12 Anas S. Sajisha VS. Mohanlal S. Radhakrishnan KV. Synlett  2006,  2399 
    Article in Thieme ConnectGoogle Scholar
  • 13 Anas S. John J. Sajisha VS. John J. Rajan R. Suresh E. Radhakrishnan KV. Org. Biomol. Chem.  2007,  5:  4010 
    CrossrefPubMedGoogle Scholar
  • 14 Anas S. Sajisha VS. John J. Joseph N. George SC. Radhakrishnan KV. Tetrahedron  2008,  64:  9689 
    CrossrefGoogle Scholar
  • 15 Luna AP. Cesario M. Bonin M. Micouin L. Org. Lett.  2003,  5:  4771 
    CrossrefPubMedGoogle Scholar
  • 16 Hand Book of Organopalladium Chemistry for Organic Synthesis   Vol. 2:  Negishi E. Wiley-Interscience; New York: 2002. 
    Google Scholar