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Synthesis 2004(3): 409-414  
DOI: 10.1055/s-2004-815936
PAPER
© Georg Thieme Verlag Stuttgart · New York

A Cross Metathesis Based Protocol for the Effective Synthesis of Function­alised Allyl Bromides and Chlorides

Marco Bandini, Pier Giorgio Cozzi*, Sebastiano Licciulli, Achille Umani-Ronchi*
Dipartimento di Chimica ‘G. Ciamician’, Università di Bologna, Via Selmi 2, 40126 Bologna, Italy
Fax: +39(51)2099456; e-Mail: piergiorgio.cozzi@ciam.unibo.it; e-Mail: umanironchi@ciam.unibo.it;
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Publikationsverlauf

Received 3 December 2003
Publikationsdatum:
26. Januar 2004 (online)

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Abstract

Functionalised allyl halides, useful starting materials for the preparation of substituted organometallic reagents can be simply obtained by a straightforward approach. Hoveyda’s ruthenium carbene catalyst 3, used in catalytic amount (2 mol%), is able to promote the cross metathesis of allyl bromide and chloride with a variety of different substituted olefins giving the corresponding functionalised allyl halides in satisfactory yields. trans-Olefins are obtained as major diastereoisomers reaching 90:10 (trans:cis) ratio when allyl chloride is used as the metathesis partner. This reaction represents a simple and accessible way for the preparation of valuable precursors for functionalised organometallic reagents. In particular, the use of functionalised allyl bromides (10b and 13) in the enantioselective Nozaki-Hiyama reaction promoted by [Cr(Salen)Cl] is presented.

Key words

allyl halides - cross metathesis - ruthenium catalyst - functionalised olefins

    References

  • 1a Schwab P. France MB. Ziller JW. Grubbs RH. Angew. Chem., Int. Ed. Engl.  1995,  34:  2039 
    Google Scholar
  • 1b Schwab P. Ziller JW. Grubbs RH. J. Am. Chem. Soc.  1996,  118:  100 
    Google Scholar
  • 2a Schrock RR. Murdzek LS. Bazan GC. Robbins J. DiMare M. O’Regan M. J. Am. Chem. Soc.  1990,  112:  3875 
    CrossrefGoogle Scholar
  • 2b Fu GC. Grubbs RH. J. Am. Chem. Soc.  1992,  114:  7324 
    CrossrefGoogle Scholar
  • 3a Scholl M. Ding S. Lee CW. Grubbs RH. Org. Lett.  1999,  1:  953 
    Google Scholar
  • 3b Chatterjee AK. Grubbs RH. Org. Lett.  1999,  1:  1751 
    Google Scholar
  • 3c Chatterjee AK. Morgan JP. Scholl M. Grubbs RH. J. Am. Chem. Soc.  2000,  122:  3783 
    Google Scholar
  • 4 Garber SB. Kingsbury JS. Gray BL. Hoveyda AH. J. Am. Chem. Soc.  2000,  122:  8168 
    Google Scholar
  • 5 Brümmer O. Rückert A. Blechert S. Chem.-Eur. J.  1997,  3:  441 
    Google Scholar
  • 6 Grela K. Bieniek M. Tetrahedron Lett.  2001,  42:  6425 
    CrossrefGoogle Scholar
  • 7 Langer P. Holtz E. Synlett  2001,  110 
    Google Scholar
  • 8 Engelhart FC. Schmitt MJ. Taylor RE. Org. Lett.  2001,  3:  2209 
    CrossrefGoogle Scholar
  • 9 Imhof S. Randl S. Blechert S. Chem. Commun.  2001,  1692 
    CrossrefGoogle Scholar
  • 10a Gessler S. Randl S. Blechert S. Tetrahedron Lett.  2000,  41:  9973 
    CrossrefGoogle Scholar
  • 10b Rivard M. Blechert S. Eur. J. Org. Chem.  2003,  2225 
    CrossrefGoogle Scholar
  • 11a Choi T.-L. Chatterjee AK. Grubbs RH. Angew. Chem. Int. Ed.  2001,  40:  1277 
    CrossrefGoogle Scholar
  • 11b Cossy J. BouzBouz S. Hoveyda AH. J. Organomet. Chem.  2001,  634:  216 
    CrossrefGoogle Scholar
  • 12 Blechert S. Connon SJ. Angew. Chem. Int. Ed.  2003,  42:  1900 
    Google Scholar
  • 13 Bandini M. Cozzi PG. Umani-Ronchi A. Chem. Commun.  2002,  919 ; and references therein
    CrossrefGoogle Scholar
  • 14a Trnka TM. Day MW. Grubbs RH. Angew. Chem. Int. Ed.  2001,  40:  3441 ; and references therein
    CrossrefGoogle Scholar
  • 14b Goldberg SD. Grubbs RH. Angew. Chem. Int. Ed.  2002,  41:  807 
    CrossrefGoogle Scholar
  • 15 Blanco OM. Castedo L. Synlett  1999,  557 
    Artikel in Thieme ConnectGoogle Scholar
  • 16 Liu B. Das SK. Roy R. Org. Lett.  2002,  4:  2723 
    CrossrefGoogle Scholar
  • 17 Elemes Y. Foote CS. J. Am. Chem. Soc.  1992,  114:  6044 
    CrossrefGoogle Scholar
  • 18 Van der Schaaf PA. Kolly R. Kirner H.-J. Rime F. Mühlebach A. Hafner A. J. Organomet. Chem.  2000,  606:  65 
    CrossrefGoogle Scholar
  • 19 The use of trans-1,3-dibromo or trans-1,3-dichloropropene does not improve the yield causing instead the failure of the reaction. For this strategy see: Blackwell HE. O’Leary DJ. Chatterjee AK. Washenfelder RA. Bussmann DA. Grubbs RH. J. Am. Chem. Soc.  2000,  122:  5871 
    Google Scholar
  • Selected examples:
  • 20a [Sn]: Marshall JA. In Organometallic in Synthesis: A Manual   Schlosser M. Wiley; Chichester: 2002.  p.353 
    Google Scholar
  • 20b [Ti]: Reetz MT. In Organometallic in Synthesis: A Manual   Schlosser M. Wiley; Chichester: 2002.  p.817 
    Google Scholar
  • 20c [Zn]: Nakamura E. In Organometallic in Synthesis: A Manual   Schlosser M. Wiley; Chichester: 2002.  p.353 
    Google Scholar
  • 20d [Cu]: Lipshutz BH. In Organometallic in Synthesis: A Manual   Schlosser M. Wiley; Chichester: 2002.  p.665 
    Google Scholar
  • 21 Yamamoto Y. Takahashi M. Miyaura N. Synlett  2002,  128 
    Artikel in Thieme ConnectGoogle Scholar
  • 22 Fürstner A. Shi N. J. Am. Chem. Soc.  1996,  118:  12349 ; and references therein.
    Google Scholar
  • 23 Bandini M. Cozzi PG. Umani-Ronchi A. Angew. Chem. Int. Ed.  2000,  39:  2327 
    CrossrefGoogle Scholar
  • 24 Bandini M. Cozzi PG. Melchiorre P. Morganti S. Umani-Ronchi A. Org. Lett.  2001,  3:  1153 
    CrossrefGoogle Scholar
  • 25 Very recently, a highly stereoselective addition of 3-chloropropenyl pivaloate to aldehydes in the presence of [Cr(Salen)]-TMSCl-Mn catalytic system was reported: Lombardo M. Licciulli S. Morganti S. Trombini C. Chem. Commun.  2003,  1762 
    CrossrefGoogle Scholar
  • Recently, Grela and Blechert have reported new tailored highly active catalysts for the CM reactions, see:
  • 26a Grela K. Harutyunyan S. Michrowska A. Angew. Chem. Int. Ed.  2002,  41:  4038 
    CrossrefGoogle Scholar
  • 26b Connon SJ. Dunne AM. Blechert S. Angew. Chem. Int. Ed.  2002,  41:  3835 
    CrossrefGoogle Scholar