A Short Enantiosynthesis of Dioxaspiroacetalic Semiochemicals by Using Chiral Building-Blocks from rac-1,n-Alkanediols by Lipase-Mediated Resolution [1]

Abstract

(2R,6S,8R)-2,8-Dimethyl-1,7-dioxaspiro[5.5]undecane (1a) and its enantiomer 1b, have been synthesized by Wittig’s methodology using the ylide from acetone-1,3-bis(triphenylphosphonium) chloride and the appropriately protected aldehydes from chiral 1,3-butanediols. The latter are prepared by a chemoenzymatic resolution procedure.

Key words

pheromones - enantiomeric resolution - lipases - diols - ylides - spiro compounds

References

• 1 Izquierdo I. Plaza M.-T. Rodríguez M. Tamayo J.-A. Martos A. Tetrahedron: Asymmetry  2001,  12:  293 
• 2a Bergström G. Tengö J. Reith W. Francke W. Z. Naturforsch., C: Biosci.  1982,  37:  1124 
• 2b Tengö J. Lennart A. Baur B. Isacksson R. Liljefors T. Mori K. König W. Francke W. J. Chem. Ecol.  1990,  16:  429 
• 3 Francke W. Kitching W. Curr. Org. Chem.  2001,  5:  233 
• 4a By alkylation with chiral templates: Mori K. Tanida K. Tetrahedron  1981,  37:  3221 
• 4b Mori K. Watanabe H. Tetrahedron  1986,  42:  295 
• 4c Perkins MV. Kitching W. König WA. Drew RAI. J. Chem. Soc., Perkin Trans. 1  1990,  2501 
• 4d Yadav JS. Gadgil VR. Tetrahedron Lett.  1990,  31:  6217 
• 4e Cohen T. Tong S. Tetrahedron  1997,  53:  9487 
• 4f By reduction of a chiral diketodisulfoxide: Solladie G. Huser N. Tetrahedron: Asymmetry  1994,  5:  255 
• 4g By Sharpless dihydroxylation of a ketodiene: Sauret S. Cuer A. Gourcy J.-G. Jeminet G. Tetrahedron: Asymmetry  1995,  6:  1995 
• 4h By hydroboration of chiral homoallylic alcohols: Brown HC. Kulkarni SV. Racherla US. Dhokte UP. J. Org. Chem.  1998,  63:  7030 
• 5 Denney DB. Song J. J. Org. Chem.  1964,  29:  495 
• 6 Enders D. Dahmen W. Dederichs E. Gatzweiler W. Weuster P. Synthesis  1990,  1013