Download PDF
Synlett 2003(4): 0532-0536
DOI: 10.1055/s-2003-37516
LETTER
© Georg Thieme Verlag Stuttgart · New York

Palladium(0)-Mediated Preparation of trans-4-Substituted-1-(phthalimido)-2-cyclopentenes [1]

Frederick A. Luzzio*, Alexander V. Mayorov
Department of Chemistry, University of Louisville, Louisville, Kentucky 40292
Fax: +1(502)8528149; e-Mail: faluzz01@athena.louisville.edu;
Further Information

Publication History

Received 24 January 2003
Publication Date:
26 February 2003 (online)

    Permissions and Reprints All articles of this category

Abstract

The series of title compounds were found to be conven­iently available from the corresponding trans-4-chloro-1-(phthalimido)-2-cyclopentene. The allylic chlorocycloalkene was found to be an excellent substrate for Pd(0)-mediated acyloxylation with the salts of carboxylic acids. Using the allylic chlorocycloalkene as a coupling partner, the Pd(0)-mediated alkylation with active methylene compounds was facilitated in variable yields by promotion with organic bases such as DBU and 1,1,3,3-tetramethylguanidine. Using the Pd(0)-mediated protocol, the product 4-substituted-trans-1-phthalimido-2-cyclopentenes were obtained in modest to excellent yields overall.

Key words

alkylation - coupling reactions - cyclopentenes - imides - palladium

1

Presented at the 221st National Meeting of the American Chemical Society, April 1-4, 2001, San Diego, California; ORGN 406.

    References

  • 2 Vogt PF. Hansel JG. Miller MJ. Tetrahedron Lett.  1997,  38:  2803 
    CrossrefGoogle Scholar
  • 3 Hodgson DM. Thompson AJ. Wadman S. Keats CJ. Tetrahedron  1999,  55:  10815 
    CrossrefGoogle Scholar
  • 4 Stragies R. Blechert S. Tetrahedron  1999,  55:  8179 
    CrossrefGoogle Scholar
  • 5a Trost BM. Madsen R. Guile SD. Brown B. J. Am. Chem. Soc.  2000,  122:  5947 
    CrossrefGoogle Scholar
  • 5b Grumann A. Marley H. Taylor RJK. Tetrahedron Lett.  1995,  36:  7767 
    CrossrefGoogle Scholar
  • 6 Clark MA. Goering BK. Li J. Ganem B. J. Org. Chem.  2000,  65:  4058 
    CrossrefPubMedGoogle Scholar
  • 7 Qiu J. Pingsterhaus JM. Silverman RB. J. Med. Chem.  1999,  42:  4725 
    CrossrefGoogle Scholar
  • 8 Trost BM. Kuo GH. Benneche T. J. Am. Chem. Soc.  1988,  110:  621 
    CrossrefGoogle Scholar
  • 9 Barrette S. O’Brien P. Steffens HC. Towers TD. Voith M. Tetrahedron  2000,  56:  9633 
    CrossrefGoogle Scholar
  • 10 Surman MD. Miller MJ. Org. Lett.  2001,  3:  519 
    CrossrefPubMedGoogle Scholar
  • 11 For a comprehensive review see: Trost BM. Van Vranken DL. Chem. Rev.  1996,  96:  395 
    Google Scholar
  • 12 Trost BM. Lee C. In Catalytic Asymmetric Synthesis   Ojima I. John Wiley; New York: 2000.  Chap. 8E. p.621-622  
    Google Scholar
  • 13 Luzzio FA. Mayorov AV. Figg WD. Tetrahedron Lett.  2000,  41:  2275 
    CrossrefGoogle Scholar
  • 14a Deardorff DR. Linde RG. Martin AM. Shulman MJ. J. Org. Chem.  1989,  54:  2759 
    Google Scholar
  • 14b Deardorff DR. Matthews AJ. McMeekin DS. Craney CL. Tetrahedron Lett.  1986,  27:  1255 
    Google Scholar
  • 14c Deardorff DR. Myles DC. MacFerrin KD. Tetrahedron Lett.  1985,  26:  5615 
    Google Scholar
  • 15 Oppolzer W. Gaudin JM. Birkinshaw TN. Tetrahedron Lett.  1988,  29:  4705 
    CrossrefGoogle Scholar
  • 16a The allylic chloride, 2-cyclopentenyl chloride, has been found to be an effective coupling partner in asymmetric alkylations mediated by [(η3-C3H5)PdCl]2: Kudis S. Helmchen G. Tetrahedron  1998,  54:  10449 
    CrossrefGoogle Scholar
  • 16b For preparation and employment of a substituted cyclohexenyl allylic chloride with palladium-mediated amination, see: Kok SHL. Shing TKM. Tetrahedron Lett.  2000,  41:  6865 
    CrossrefGoogle Scholar
  • 17 Dodge JA. Nissen JS. Presnell M. In Organic Synthesis   Vol. 73:  Boeckman RK. Wiley; New York: 1996. 
    Google Scholar
  • 19a Mulvihill MJ. Surman MD. Miller MJ. J. Org. Chem.  1998,  63:  4874 
    CrossrefGoogle Scholar
  • 19b Crimmins MT. King BW. Zuercher WJ. Choy AL. J. Org. Chem.  2000,  65:  8499 
    CrossrefGoogle Scholar
1

Presented at the 221st National Meeting of the American Chemical Society, April 1-4, 2001, San Diego, California; ORGN 406.

18

For employment of the analogous phenylsulfonylnitro-methane in palladium-mediated alkylations, see ref. 5a

20

Carbon signals marked with an asterisk (*) represent methyl and methyne carbons as determined by APT experiments.

21

Prepared from (+)-8 which was derived (Method B) from the (+)-1R, 4S-phthalimido-2-cyclopentenol prepared by method of Deardorff (ref. [14a] ).