Synthesis 2004(14): 2411-2417  
DOI: 10.1055/s-2004-829189
PSP
© Georg Thieme Verlag Stuttgart · New York

Stereoselective Synthesis and Reactivity of Dienyl Zirconocene Derivatives

Nicka Chinkov, Swapan Majumdar, Ilan Marek*
Department of Chemistry and Institute of Catalysis Science and Technology, Technion-Israel Institute of Technology Technion City, Haifa 32000, Israel
e-Mail: [email protected];
Further Information

Publication History

Received 26 April 2004
Publication Date:
30 July 2004 (online)

Abstract

Stereoselective dienyl zirconocene derivatives have been prepared via a tandem allylic C-H bond activation isomerization-elimination reaction. These reagents can be either trapped directly with electrophiles or transmetalated to copper to participate in several carbon-carbon bond formations. When the transmetalation is performed on allylic as well as vinylic zirconocene derivatives, the reaction occurs with inversion of stereochemistry of the dienyl system.

    References

  • For reviews see:
  • 1a Marek I. J. Chem. Soc., Perkin Trans. 1  1999,  535 
  • 1b Marek I. In Modern C,C- and C,X-Bond Formations by Metal-Catalyzed Cross-Coupling Reactions   de Meijere A. Diederich F. Wiley-VCH; Weinheim, Germany: 2004.  p.in press 
  • 1c Marek I. In Transition Metals for Organic Synthesis   2nd ed.:  Beller M. Bolm C. Wiley-VCH; Weinheim, Germany: 2004.  p.in press 
  • 1d Marek I. Normant JF. In Metal-Catalyzed Cross Coupling Reactions   Diederich F. Stang PJ. Wiley-VCH; Weinheim, Germany: 1998.  p.271 
  • 1e Normant JF. Alexakis A. Synthesis  1981,  841 
  • 1f Knochel P. In Comprehensive Organic Synthesis   Vol. 4:  Trost BM. Fleming I. Semmelhack MF. Pergamon Press; New York: 1991.  p.865 
  • 1g Negishi E. Pure Appl. Chem.  1981,  53:  2333 
  • 1h Fallis AG. Forgione P. Tetrahedron  2001,  57:  5899 
  • 2a Forgione P. Wilson PD. Fallis AG. Tetrahedron Lett.  2000,  41:  17 
  • 2b Forgione P. Wilson PD. Yap GPA. Fallis AG. Synthesis  2000,  921 
  • 2c Alexakis A. Normant JF. Tetrahedron Lett.  1982,  23:  5151 
  • 2d Furber M. Taylor RJK. Burford SC. J. Chem. Soc., Perkin Trans 1  1986,  1809 
  • 3 Negishi E. In Titanium and Zirconium in Organic Synthesis   Marek I. VCH; Weinheim, Germany: 2002.  p.1 
  • 4 Liard A. Marek I. J. Org. Chem.  2000,  65:  7218 
  • 5 Farhat S. Marek I. Angew. Chem. Int. Ed.  2002,  41:  1410 
  • 6a Liard A. Chechik H. Farhat S. Morlender-Vais N. Averbuj C. Marek I. J. Organomet. Chem.  2001,  624:  26 
  • 6b Chinkov N. Chechik H. Majumdar S. Marek I. Synthesis  2002,  2473 
  • 7a Swanson DR. Negishi E. Organometallics  1991,  10:  825 
  • 7b Maye JP. Negishi E. Tetrahedron Lett.  1993,  34:  3359 
  • 7c Negishi E. Maye JP. Choueiry D. Tetrahedron  1995,  51:  4447 
  • 8a Chinkov N. Majumdar S. Marek I. J. Am. Chem. Soc.  2002,  124:  10282 
  • 8b Chinkov N. Majumdar S. Marek I. J. Am. Chem. Soc.  2003,  125:  13258 
  • 9 Alexakis A. Normant JF. Isr. J. Chem.  1984,  24:  113 
  • 10a Cuvigny T. Herve du Penhoat C. Julia M. Tetrahedron  1986,  42:  5329 
  • 10b Backvall JE. Chinchilla R. Najera C. Yus M. Chem. Rev.  1998,  98:  2291 
  • 11a Mintz EA. Ward AS. Tice DS. Organometallics  1985,  4:  1308 
  • 11b Ward AS. Mintz EA. Kramer MP. Organometallics  1988,  7:  8 
  • 12 Rozema MJ. Knochel P. Tetrahedron Lett.  1991,  32:  185 
  • 13a Nakamura E. Kuwajima I. J. Am. Chem. Soc.  1984,  106:  3368 
  • 13b Corey EJ. Boaz NW. Tetrahedron Lett.  1985,  26:  6015 
  • 13c Alexakis A. Berlan J. Besace Y. Tetrahedron Lett.  1986,  27:  2143