Synthesis and absolute stereochemistry of spiroacetals in rove beetles (Coleoptera: Staphylinidae)

Tetrahedron Letters

Volumn 40, Issue 44, 1999, Pages 7851-7854

  Zhang, Hesheng ^a   Fletcher, Mary T ^a   Dettner, Konrad ^b   Francke, Wittko ^c   Kitching, William ^a  

^a UNIVERSITY OF QUEENSLAND   (Australia)

^b UNIVERSITY OF BAYREUTH   (Germany)

^c UNIVERSITY OF HAMBURG   (Germany)

Author keywords

Enantioselective chromatography; Insect; Spiroacetal

Indexed keywords

SPIRO COMPOUND;

ARTICLE; BEETLE; CHROMATOGRAPHY; ENANTIOMER; ISOMER; RACEMIC MIXTURE; STEREOCHEMISTRY; STRUCTURE ANALYSIS; SYNTHESIS;

COLEOPTERA; INSECTA; ONTHOLESTES; STAPHYLINIDAE;

EID: 0033615786     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)01612-3     Document Type: Article

References (17)

1. 1. Dettner, K.; Schwinger, G. Z. Naturforsch 1986, 42c, 366.
2. 2. Francke, W.; Hindorf, G.; Reith, W. Naturwissenschaften 1979, 66, 618. Comparison with the mass spectra of known spiroacetals with M=198 showed no coincidence. A notable feature of the mass spectrum of the unknown compound was the relatively high abundance of the M-15 ion (m/z 183), when compared with the M-15 ion for 1. This indicated an especially stabilised oxonium ion, possibly arising from methyl loss from a gem-dimethyl group adjacent to oxygen. For a plotted 70 ev mass spectrum of (E,E)-1, see: Francke, W.; Reith, W.; Bergström, G.; Tengö, J. Naturwissenschaften 1980, 67, 619.
3. 2. Francke, W.; Hindorf, G.; Reith, W. Naturwissenschaften 1979, 66, 618. Comparison with the mass spectra of known spiroacetals with M=198 showed no coincidence. A notable feature of the mass spectrum of the unknown compound was the relatively high abundance of the M-15 ion (m/z 183), when compared with the M-15 ion for 1. This indicated an especially stabilised oxonium ion, possibly arising from methyl loss from a gem-dimethyl group adjacent to oxygen. For a plotted 70 ev mass spectrum of (E,E)-1, see: Francke, W.; Reith, W.; Bergström, G.; Tengö, J. Naturwissenschaften 1980, 67, 619.
4. 3. Huth, A.; Dettner, K. J. Chem. Ecol. 1990, 16, 2691.
5. 4. Francke, W. Les Mediateurs Chimiques; INRA: Versailles, 1982; p. 81.
6. 5. Fletcher, M. T.; Kitching, W. Chem. Rev. 1995, 95, 789.
7. 6. Francke, W.; Kitching, W. Current Organic Chemistry 1999, in press. Thirty different spiroacetal structures, not including stereoisomers, are known from insects.
8. 7. Moore, C. J.; Hubener, A.; Tu, Y. Q.; Kitching, W.; Aldrich, J. R.; Waite, G. K.; Schulz, S.; Francke, W. J. Org. Chem. 1994, 59, 6136.
9. 8. Tu, Y. Q.; Moore, C. J.; Kitching, W. Tetrahedron: Asymmetry 1995, 6, 397.
10. 9. Jacobson, R.; Taylor, R. J.; Williams, H. J.; Smith, L. R. J. Org. Chem. 1982, 47, 3140, and references cited therein.
11. 3) δ: 15.8, 19.2, 21.5, 25.3, 32.8, 32.9, 36.4, 37.1, 37.2, 65.7, 72.0, 96.2.
12. 11. (a) Mori, K.; Watanabe, H. Tetrahedron 1986, 42, 295.
13. (b) Perkins, M. V.; Jacobs, M. F.; Kitching, W.; Cassidy, P. J.; Lewis, J. A.; Drew, R. A. I. J. Org. Chem. 1992, 57, 3365.
14. 12. See, for example: Perkins, M. V.; Kitching, W.; König, W. A.; Drew, R. A. I. J. Chem. Soc., Perkin Trans. 1 1990, 2501.
15. 13. Spiroacetals with S chirality at the spirocentre are dextrorotatory. See: Mori, K.; Ikunaka, M. Liebigs Ann. Chem. 1987, 333.
16. 14. Hungerford, N. L.; Mazomenos, B. E.; Konstantopoulou, M. A.; Krokos, F. D.; Haniotakis, G. E.; Hübener, A.; Fletcher, M. T.; Moore, C. J.; DeVoss, J. J.; Kitching, W. Chem. Commun. 1998, 863.
17. 15. Dettner, K.; Fettköther, R.; Ansteeg, O.; Demi, R.; Liepert, C.; Petersen, B.; Haslinger, E.; Francke, W. J. Appl. Ent. 1992, 113, 128.