Synthesis 2005(14): 2449-2452  
DOI: 10.1055/s-2005-872089
PSP
© Georg Thieme Verlag Stuttgart · New York

Highly Diastereoselective Michael Additions onto Dienyl Bis-Sulfoxides

Franck Brebion, Jean Philippe Goddard, Louis Fensterbank*, Max Malacria*
Université Pierre et Marie Curie, UMR CNRS 7611, Institut de chimie moleculaire, FR 2769, case 229, 4 place Jussieu, 75252 Paris cedex 05, France
e-Mail: louis.fensterbank@upmc.fr; e-Mail: max.malacria@upmc.fr;
Further Information

Publication History

Received 14 March 2005
Publication Date:
20 July 2005 (eFirst)

Abstract

An optimized procedure for the preparation of (S S,S S)-bis(p-tolylsulfinyl)methane (4) is reported. Condensation of the lithium salt of 4 onto cinnamaldehyde furnished bis-sulfoxide dienyl derivative 5, a remarkable 1,4-Michael acceptor that can lead in a highly dia­stereoselective manner to vinylcyclopropyl adducts. In a chelating mode of reactivity using a methylcopper reagent, a complete reversal of stereoselectivity is observed giving an enantiopure β,γ-unsaturated methyl ester intermediate that is used in the synthesis of cryptophycin.

    References

  • 1 For a review on bis-sulfoxides, see: Delouvrié B. Fensterbank L. Nájera F. Malacria M. Eur. J. Org. Chem.  2002,  3507 
  • 2 For an article dealing with the preparation of substrates 1, see: Delouvrié B. Nájera F. Fensterbank L. Malacria M. J. Organomet. Chem.  2002,  643-644:  130 
  • 3 Brebion F. Vitale M. Fensterbank L. Malacria M. Tetrahedron: Asymmetry  2003,  14:  2889 
  • 4 Brebion F. Delouvrié B. Nájera F. Fensterbank L. Malacria M. Vaissermann J. Angew. Chem. Int. Ed.  2003,  42:  5342 
  • 5 Solladié G. Colobert F. Ruiz P. Hamdouchi C. Carreño MC. Garcia Ruano JL. Tetrahedron Lett.  1991,  32:  3695 
  • 6 Evans DA. Bryan CA. Sims CL. J. Am. Chem. Soc.  1972,  94:  2891 
  • 7 Solladié G. Hutt J. Girardin A. Synthesis  1987,  173 
  • 8 Kunieda N. Nokami J. Kinoshita M. Bull. Chem. Soc. Jpn.  1976,  49:  256 
  • 9 Krause N. Hoffmann-Röder A. In Modern Organocopper Chemistry   Krause N. Wiley-VCH; Weinheim: 2002.  p.145-166  
  • 10 Salamonczyk GM. Han K. Guo Z.-W. Sih CJ. J. Org. Chem.  1996,  61:  6893