Download PDF
Synthesis 2011(12): 1988-1992  
DOI: 10.1055/s-0030-1260467
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Towards a Catalytic Asymmetric Version of the [3+2] Cycloaddition between Hydrazones and Cyclopentadiene

Alexandru Zamfir, Svetlana B. Tsogoeva*
Department of Chemistry and Pharmacy, Institute of Organic Chemistry I, University of Erlangen-Nuremberg, Henkestr. 42, 91054 Erlangen, Germany
Fax: +49(9131)8526865; e-Mail: tsogoeva@chemie.uni-erlangen.de;
Further Information

Publication History

Received 12 April 2011
Publication Date:
17 May 2011 (online)

   Permissions and Reprints All articles of this category

Abstract

A novel and easily accessible metal-free catalytic system, an in situ generated BINOL-phosphate-derived silicon Lewis acid, has been described for the [3+2] cycloaddition of N-benzoylhydrazone to cyclopentadiene to afford a cycloadduct in high dia­stereomeric ratio of 95:5 (syn/anti) and enantiomeric excess of 89%. These results provide insights in the future design and development of highly active and enantioselective silicon Lewis acids for this and other cycloaddition types.

Key words

cycloaddition - silicon - hydrazones - Lewis acids - nitrogen heterocycles

    References

  • 1a Rajendra Prasad Y. Lakshmana Rao A. Prasoona L. Murali K. Ravi Kumar P. Bioorg. Med. Chem. Lett.  2005,  15:  5030 
    Search in Google Scholar
  • 1b Jeong T.-S. Kim KS. An S.-J. Cho K.-H. Lee S. Lee WS. Bioorg. Med. Chem. Lett.  2004,  14:  2715 
    Search in Google Scholar
  • 1c Gürsoy A. Demirayak Ş. Capan G. Erol K. Vural K. Eur. J. Med. Chem.  2000,  35 
  • 1d Özdemir A. Turan-Zitouni G. Kaplancikli ZA. Revial G. Güven K. Eur. J. Med. Chem.  2007,  42:  403 
    Search in Google Scholar
  • 1e Brozozowski Z. Sączewski F. Gdaniec M. Eur. J. Med. Chem.  2000,  35:  1053 
    Search in Google Scholar
  • 1f Kornet MJ. Garrett RJ. J. Pharm. Sci.  1979,  68:  377 
    Search in Google Scholar
  • 1g Özdemir Z. Kandilici HB. Gümüºel B. Caliº Ü. Bilgin AA. Eur. J. Med. Chem.  2007,  42:  373 
    Search in Google Scholar
  • 1h Harrison CR, and Lahm GP. inventors; Patent WO  91/11438.  ; Chem. Abstr. 1991, 115, 207988
  • For examples of [3+2] cycloaddition of hydrazones with olefins under acidic conditions, see:
  • 2a Hesse K.-D. Liebigs Ann. Chem.  1970,  743:  50 
    Search in Google Scholar
  • 2b Fevre GL. Sinbandhit S. Hamelin J. Tetrahedron  1979,  35:  1821 
    Search in Google Scholar
  • 2c Fouchet B. Joucla M. Hamelin J. Tetrahedron Lett.  1981,  22:  1333 
    Search in Google Scholar
  • 2d Shimizu T. Hayashi Y. Ishikawa S. Teramura K. Bull. Chem. Soc. Jpn.  1982,  55:  2450 
    Search in Google Scholar
  • 2e Shimizu T. Hayashi Y. Miki M. Teramura K. J. Org. Chem.  1987,  52:  2277 
    Search in Google Scholar
  • For examples of [3+2] cycloaddition of hydrazones with olefins under thermal conditions, see:
  • 3a Grigg R. Kemp J. Thompson N. Tetrahedron Lett.  1978,  2827 
  • 3b Grigg R. Dowling M. Jordan MW. Sridharan V. Tetrahedron  1987,  43:  5873 
    Search in Google Scholar
  • 3c Snider BB. Conn RSE. Sealfon S. J. Org. Chem.  1979,  44:  218 
    Search in Google Scholar
  • 3d Le Fevre G. Hamelin J. Tetrahedron Lett.  1979,  20:  1757 
    Search in Google Scholar
  • 3e Ibrahim YA. Abdou SE. Selim S. Heterocycles  1982,  19:  819 
    Search in Google Scholar
  • 3f Badawy MA. El-Bahaie SA. Kadry AM. Ibrahim YA. Heterocycles  1988,  27:  7 
    Search in Google Scholar
  • 3g Khau VV. Martinelli MJ. Tetrahedron Lett.  1996,  37:  4323 
    Search in Google Scholar
  • 3h Sun B. Adachi K. Noguchi M. Tetrahedron  1996,  52:  901 
    Search in Google Scholar
  • 4a Kobayashi S. Hirabaysahi R. Shimizu H. Ishitani H. Yamashita Y. Tetrahedron Lett.  2003,  44:  3351 
    Search in Google Scholar
  • 4b Kobayashi S. Shimizu H. Yamashita Y. Ishitani H. Kobayashi J. J. Am. Chem. Soc.  2002,  124:  13678 
    Search in Google Scholar
  • 4c Yamashita Y. Kobayashi S. J. Am. Chem. Soc.  2004,  126:  11279 
    Search in Google Scholar
  • 5a Müller S. List B. Angew. Chem. Int. Ed.  2009,  48:  9975 ; Angew. Chem. 2009, 121, 10160
    Search in Google Scholar
  • 5b Müller S. List B. Synthesis  2010,  2171 
  • 6a Shirakawa S. Lombardi PJ. Leighton JL. J. Am. Chem. Soc.  2005,  127:  9974 
    Search in Google Scholar
  • 6b Leighton JL, Berger R, and Shirakawa S. inventors; PCT Int. Appl.  WO 2006062901.  ; Chem. Abstr. 2006, 145, 46186
  • For general reviews, see:
  • 7a Dalko PI. Moisan L. Angew. Chem. Int. Ed.  2001,  40:  3726 ; Angew. Chem. 2001, 113, 3840
    Search in Google Scholar
  • 7b Dalko PI. Moisan L. Angew. Chem. Int. Ed.  2004,  43:  5138 ; Angew. Chem. 2004, 116, 5248
    Search in Google Scholar
  • 7c Houk KN. List B. Acc. Chem. Res.  2004,  37:  487 
    Search in Google Scholar
  • 7d Berkessel A. Gröger H. Asymmetric Organocatalysis   Wiley-VCH; Weinheim: 2005. 
  • 7e List B. Yang JW. Science  2006,  313:  1584 
    Search in Google Scholar
  • 7f Enantioselective Organocatalysis   Dalko PI. Wiley-VCH; Weinheim: 2007. 
  • 7g Pellissier H. Tetrahedron  2007,  63:  9267 
    Search in Google Scholar
  • 7h Dondoni A. Massi A. Angew. Chem. Int. Ed.  2008,  47:  4638 ; Angew. Chem. 2008, 120, 4716
    Search in Google Scholar
  • 7i Melchiorre P. Marigo M. Carlone A. Bartoli G. Angew. Chem. Int. Ed.  2008,  47:  6138 ; Angew. Chem. 2008, 120, 6232
    Search in Google Scholar
  • 8a Chuit C. Corriu RJP. Reye C. Young JC. Chem. Rev.  1993,  93:  1371 
    Search in Google Scholar
  • 8b Uhlig W. Chem. Ber.  1996,  129:  733 
    Search in Google Scholar
  • 8c Holmes RR. Chem. Rev.  1996,  96:  927 
    Search in Google Scholar
  • 8d Rendler S. Oestreich M. Synthesis  2005,  1727 
  • 8e Sereda O. Tabassum S. Wilhelm R. Top. Curr. Chem.  2009,  291:  349 
    Search in Google Scholar
  • 9a Yalalov DA. Tsogoeva SB. Shubina TE. Martynova IM. Clark T. Angew. Chem. Int. Ed.  2008,  47:  6624 ; Angew. Chem. 2008, 120, 6726
    Search in Google Scholar
  • 9b Tsogoeva SB. Wei S.-W. Freund M. Mauksch M. Angew. Chem. Int. Ed.  2009,  48:  590 ; Angew. Chem. 2009, 121, 598
    Search in Google Scholar
  • 9c Zamfir A. Tsogoeva SB. Org. Lett.  2010,  12:  188 
    Search in Google Scholar
  • 9d For an excellent review on the chemistry of N-acyl-hydrazones, see: Sugiura M. Kobayashi S. Angew. Chem. Int. Ed.  2005,  44:  5176 ; Angew. Chem. 2005, 117, 5306
    Search in Google Scholar
  • 10 Zamfir A. Schenker S. Bauer W. Clark T. Tsogoeva SB. Eur. J. Org. Chem.  2011, DOI: 10.1002/ejoc.201100206
  • 12 Schenker S. Zamfir A. Freund M. Tsogoeva SB. Eur. J. Org. Chem.  2011,  2209 
11

3-Phenylpropionaldehyde derived hydrazones with other protecting groups like BOC (tert-butyloxycarbonyl) or Ac(acetyl) showed no or little reactivity.