Download PDF
Synthesis 2009(19): 3279-3284  
DOI: 10.1055/s-0029-1216959
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of β-Oxabutyrolactams Starting from 2,5-Dihydrooxazoles

Katharina Johannes, Jürgen Jakob, Mostafa Hatam, Jürgen Martens*
Institute of Pure and Applied Chemistry, University of Oldenburg, Carl-von-Ossietzky-Straße 9-11, 26129 Oldenburg, Germany
Fax: +49(441)7983757; e-Mail: juergen.martens@uni-oldenburg.de;
Further Information

Publication History

Received 14 April 2009
Publication Date:
21 August 2009 (online)

    Permissions and Reprints All articles of this category

Abstract

A new synthetic pathway to generate β-oxabutyrolactams starting from 2,5-dihydrooxazoles is described. This procedure is based on the addition of acid chlorides to heterocyclic imines followed by oxidation in the presence of pyridinium chlorochromate.

Key words

heterocycles - imines - β-oxabutyrolactams - oxidation - N-acyliminium ion

    References

  • 1 Karrer F. inventors; Eur. Pat. Appl. EP  79850.  ; Chem. Abstr. 1983, 99, 123617
  • 2 Middleton WJ. inventors; US  3690862.  ; Chem. Abstr. 1972, 78, 12689
  • 3 Saito T, Murayama T, Matsumoto T, and Miura T. inventors; Eur. Pat. Appl. EP  974582.  ; Chem. Abstr. 2000, 132, 107824
  • 4a Eichenberger K. Ganz E. Druey J. Helv. Chim. Acta  1955,  38:  284 
    Google Scholar
  • 4b Hiskey RG. Jung JM. J. Am. Chem. Soc.  1963,  85:  578 
    Google Scholar
  • 4c Roush WR. Essenfeld AP. Warmus JS. Brown BB. Tetrahedron Lett.  1989,  30:  7305 
    Google Scholar
  • 4d Thompson AM. Blunt JW. Munro MHG. Clark BM. J. Chem. Soc., Perkin Trans. 1  1994,  1025 
    Google Scholar
  • 5a Holzgrabe U. Pharm. Unserer Zeit  2006,  35:  410 
    Google Scholar
  • 5b Elander RP. Appl. Microbiol. Biotech.  2003,  61:  385 
    Google Scholar
  • 6 Weber M. Jakob J. Martens J. Liebigs Ann. Chem.  1992,  1 
    CrossrefGoogle Scholar
  • 7 Harada K. Additions to the azomethine group, In The chemistry of the carbon-nitrogen double bond   Patai S. John Wiley & Sons; London: 1970.  p.255 
    Google Scholar
  • 8 Yazici A. Pyne SG. Synthesis  2009,  339 
    Article in Thieme ConnectGoogle Scholar
  • 9 Speckamp WN. Hiemstra H. Tetrahedron  1985,  41:  4367 
    CrossrefGoogle Scholar
  • 10 James TC. Judd CW. J. Chem. Soc., Trans.  1914,  105:  1427 
    CrossrefGoogle Scholar
  • 11 Leuchs H. Wulkow G. Gerland H. Chem. Ber.  1932,  62:  1586 
    Google Scholar
  • 12 Maryanoff BE. Zhang H.-C. Cohen JH. Turchi IJ. Maryanoff CA. Chem. Rev.  2004,  104:  1431 
    CrossrefPubMedGoogle Scholar
  • 13 Bose AK. Spiegelman G. Manhas MS. Tetrahedron Lett.  1971,  34:  3167 
    Google Scholar
  • 16 Belyaev A. Borloo M. Augustyns K. Lambeir A.-M. De Meester I. Scharpé S. Blaton N. Peeters OM. De Ranter C. Haermers A. Tetrahedron Lett.  1995,  36:  3755 
    CrossrefGoogle Scholar
  • 17 Hatam M. Tehranfar D. Martens J. Synthesis  1994,  619 
    Article in Thieme ConnectGoogle Scholar
14

In the major diastereomers, saturation of the protons of the methyl moiety at C5 generates a very small NOE for the proton at C4, indicating trans-configuration. Compared to the ROE experiments of the minor diastereomers, the saturation of the protons of the methyl moiety at C5 led to a strong NOE for the proton at C4, consequently indicating cis-configuration.

15

Saturation of the protons of the methyl group at C5 (˜1 ppm) gave a strong NOE for the proton at C4 and a moderate NOE for the proton at C2, indicating cis-configuration for the protons at C2 and C4.