Download PDF
Synthesis 2001(6): 0952-0956
DOI: 10.1055/s-2001-13397
SPECIALTOPIC
© Georg Thieme Verlag Stuttgart · New York

Novel O- and N-Linked Inositol Oligomers: A New Class of Unnatural Saccharide Mimics

Bernhard J. Paul, Theodore A. Martinot, Jerremey Willis, Tomas Hudlicky*
Department of Chemistry, University of Florida, PO Box 117200, Gainesville, Florida, 32611, USA
e-Mail: hudlicky@chem.ufl.edu;
Further Information

Publication History

Received 17 March 2001
Publication Date:
24 September 2004 (online)

    Permissions and Reprints All articles of this category

Abstract

Several N- as well as O-linked inositol oligomers were synthesized by a chemo-enzymatic approach. Whole-cell fermentation of bromobenzene with E. coli JM109(pDTG601) furnished a chiral cis-dienediol which was converted into its vinyl epoxide and vinyl aziridine, respectively. Two-fold epoxide/aziridine openings catalyzed by Yb(OTf)3 served as the key step in the synthesis of N-linked analogs, whereas a convergent approach furnished the O-linked inositol oligomers. Their synthesis is described and structural comparisons drawn to higher oligomers of l-chiro- and neo-inositol oligomers.

Key words

oligosaccharides - ring-opening - epoxides - aziridines - inositols

    References

  • 1 Gabius H.-J. Naturwissenschaften  2000,  87:  108 
    CrossrefGoogle Scholar
  • 2 Sears P. Wong C.-H. Angew. Chem., Int. Ed.  1999,  38:  2300 
    Google Scholar
  • 3 Hudlicky T. Abboud KA. Entwistle DA. Fan R. Maurya R. Thorpe AJ. Bolonick J. Myers B. Synthesis  1996,  897 
    Article in Thieme ConnectGoogle Scholar
  • 4 vanAlmsick M. Dolhaine H. Hönig H. MATCH  1999,  39:  21 
    Google Scholar
  • 5 Hudlicky T. Abboud KA. Bolonick J. Maurya R. Stanton ML. Thorpe AJ. J. Chem. Soc., Chem. Commun.  1996,  1717 
    Google Scholar
  • For synthesis and evaluation of antiglycosidic properties of similar compounds see:
  • 6a Desjardins M. Lallemand M.-C. Freeman S. Hudlicky T. Abboud KA. J. Chem. Soc., Perkin Trans. 1  1999,  621 
    Article in Thieme ConnectGoogle Scholar
  • 6b Desjardins M. Lallemand M.-C. Hudlicky T. Abboud KA. Synlett  1997,  728 
    Article in Thieme ConnectGoogle Scholar
  • 7a Gibson DT. Hensley M. Yoshioka H. Mabry TJ. Biochemistry  1970,  9:  1626 
    Google Scholar
  • 7b Hudlicky T. Luna H. Barbieri GL. Kwart LD. J. Am. Chem. Soc.  1988,  110:  4735 
    Google Scholar
  • 7c Hudlicky T. Stabile MR. Gibson DT. Whited GM. Org. Syn.  1999,  76:  77 
    Google Scholar
  • 8 Hudlicky T. Tian XR. Königsberger K. Rouden J. J. Org. Chem.  1994,  59:  4037 
    CrossrefGoogle Scholar
  • 9a Tian XR. Hudlicky T. Königsberger K. J. Am. Chem. Soc.  1995,  117:  3643 
    CrossrefGoogle Scholar
  • 9b Hudlicky T. Tian XR. Königsberger K. Maurya R. Rouden J. Fan B. J. Am. Chem. Soc.  1996,  118:  10752 
    CrossrefGoogle Scholar
  • 10 Hudlicky T. Luna H. Olivo H. Andersen C. Nugent T. Price JD. J. Chem. Soc., Perkin Trans. 1  1991,  2907 
    CrossrefGoogle Scholar
  • 13 Restrepo-Sanchez N. PhD dissertation   University of Cali; Columbia: 2001. work performed at the University of Florida
    Google Scholar
11

The ratio of 18a:18b seems to vary considerably with the reaction scale. Although we have separated 18a and 18b to establish their regiochemistry, it is not necessary to do so for preparative runs, since both ultimately yield 20.

12

These results will be reported in an upcoming full paper.

14

All molecular modeling was performed with SPARTAN SGI version 5.1.1, available from Wavefunction Inc., on a Silicon Graphics O2.