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Enantiospecific Synthesis and Chiroptical Properties of Bicyclic Enones

  1. Edvinas Orentas1,
  2. Gintautas Bagdžiūnas1,
  3. Ulf Berg2,
  4. Albinas Žilinskas1,
  5. Eugenijus Butkus1

Article first published online: 10 JUL 2007

DOI: 10.1002/ejoc.200700241

Issue

European Journal of Organic Chemistry

European Journal of Organic Chemistry

Volume 2007, Issue 25, pages 4251–4256, September 2007

Additional Information

How to Cite

Orentas, E., Bagdžiūnas, G., Berg, U., Žilinskas, A. and Butkus, E. (2007), Enantiospecific Synthesis and Chiroptical Properties of Bicyclic Enones. Eur. J. Org. Chem., 2007: 4251–4256. doi: 10.1002/ejoc.200700241

Author Information

  1. 1

    Department of Organic Chemistry, Vilnius University, Naugarduko 24, 03225 Vilnius, Lithuania, Fax: +370-5-2330987

  2. 2

    Organic Chemistry, Department of Chemistry, Lund University, P. O. Box 124, 22100 Lund, Sweden

Publication History

  1. Issue published online: 10 AUG 2007
  2. Article first published online: 10 JUL 2007
  3. Manuscript Received: 16 MAR 2007

Funded by

  • Vilnius University Science Fund
  • Nordforsk (Nordic Baltic Network in Crystal Engineering and Supramolecular Materials)

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Keywords:

  • Chirality;
  • CD spectroscopy;
  • Chromophores;
  • Enantiospecific synthesis;
  • Enones

Abstract

The enantiospecific synthesis of several bicyclic enones starting from enantiomerically pure (+)-(1S,5S)-bicyclo[3.3.1]nonane-2,6-dione (1) was accomplished. The target enones 7–9 were obtained in high yield and purity by using a catalytic amount of benzeneselenic anhydride. (+)-(1S,5R)-bicyclo[3.3.1]nonane-2,3,6-trione was obtained from diketone 1 by α-hydroxylation involving the use of iodine under basic conditions. The reaction included a ring closure/reopening sequence via oxatricyclo[4.3.1.03,8]decane-10-one. It was shown that the latter triketone exists in enone/enol form. Chiroptical properties of the enantiomerically pure compounds were studied, and the sign of the Cotton effect was related to the absolute configuration of the enones. The positive Cotton effect in the bisignate CD curve is accounted for by the nonplanarity of the chromophore in enones (1S,5R)-4 and (1S,5S)-8. The circular dichroism spectra provided evidence for interchromophoric interaction in dichromophoric bis(enone) 9. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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