Abstract
The synthesis of the title compound13 has been carried out through the preparation of its precursor, (3R,4R,5S,6R)-3,4,5-trihydroxy-1,7-dioxaspiro[5.5]undecane (6), obtained fromd-fructose using Wittig's methodology, reduction, and spiroketalation. Compound6 was transformed into13 by a Barton deoxygenation at C-5 followed by a Corey dideoxygenation at C-3,4 of the appropriately protected derivatives.
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Aamlid, K.H., Hough, L., Richardson, A.C., andHendry, D. 1987. An enantiospecific synthesis of (R)-1,4,7-trioxaspiro[5.5]undecane fromd-fructose.Carbohydr. Res. 164:373–390.
Baker, R.,Herbert, R.,Howse, P.E.,Jones, O.T.,Francke, W., andReith, W. 1980. Identification and synthesis of the major sex pheromone of the olive fly (Dacus oleae).J. Chem. Soc. Chem. Commun. 52–53.
Barton, D.H.R., andMcCombie, S.W. 1975. A new method for the deoxygenation of secondary alcohols.J. Chem. Soc. Perkin Trans. I. 1574–1585.
Brinker, U.H., Haghani, A., andGomann, K. 1985. Spiroacetal formation by carbene (carbenoid) insertion reaction: Synthesis of the major constituent of the sex attractant of the olive fly (Dacus oleae).Angew. Chem. Int. Ed. Engl. 24:230–231.
Chan, J.Y.C., Hough, L., andRichardson, A.C. 1985. The synthesis of (R)-and (S)-spirobi-1,4-dioxane and related spirobicycles from D-fructose.J. Chem. Soc. Perkin Trans. I. 1457–1462.
Corey, E.J., andWinter, R.A.E. 1963. A new stereospecific olefin synthesis from 1,2-diols.J. Am. Chem. Soc. 85:2677–2678.
DeShong, P., Waltermire, R.E., andAmmon, H.L. 1988, A general approach to the stereoselective synthesis of spiroketals. A total synthesis of the pheromones of the olive fruit fly and related compounds.J. Am. Chem. Soc. 110:1901–1910.
Deslongchamps, P., Rowan, D.D., Pothier, N., Sauvé, T., andSaunders, J.K. 1981. 1,7-Dioxaspiro[5.5]undecanes. An excellent system for the study of stereoelectronic effects (anomeric and exo-anomeric effects) in acetals.Can. J. Chem. 59:1105–1121.
Iwata, C., Fujita, M., Hattori, K., Uchida, S., andImanishi, T. 1985. Intramolecular Michael addition reaction to chiral vinylic sulfoxides. An enantioselective synthesis of (R)- and (S)-1,7-dioxaspiro[5.5]undecane.Tetrahedron Lett. 26:2221–2224.
Izquierdo Cubero, I., andPlaza Lopéz-Espinosa, M.T. 1990. An enantiospecific synthesis of (−)-talaromycins A and B from D-fructose.Carbohydr. Res. 205:293–304.
Ley, V., andLygo, B. 1984. A new route to spiroketals using the Horner-Wittig reaction of 2-diphenylphosphinoxy cyclic ethers.Tetrahedron Lett. 25:113–116.
Mori, K., Watanabe, H., Yanagi, K., andMinobe, M. 1985. Synthesis of the enantiomers of 1,7-dioxaspiro[5.5]undecane, 4-hydroxy-1,7-dioxaspiro[5.5]undecane and 3-hydroxy-1,7-dioxaspiro[5.5]undecane, the components of the olive fruit fly pheromone.Tetrahedron 41:3663–3672.
Redlich, H., andFrancke, W. 1984. Synthesis of enantiomerically pure 1,7-diox-aspiro[5.5]undecanes, pheromone components of the olive fly (Dacus oleae).Angew. Chem. Int. Ed. Engl. 23:519–520.
Smith, L.I., andSprung, J.A. 1943. Vitamin E. XLI. Synthesis of 1-chloro-3,7,11,15-tetramethylhexadecanol-3, and its condensation with trimethylhydroquinone to form α-tocopherol.J. Am. Chem. Soc. 65:1276–1283.
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Enantiospecific synthesis of spiroacetals. Part II. For Part I, see Izquierdo and Plaza (1990).
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Cubero, I.I., Plaza López-Espinosa, M.T. & Castillo, R.A. Enantiospecific synthesis of (R)-1,7-dioxaspiro [5.5]undecane [major component of olive fruit fly (Dacus Oleae) sex pheromone] from d-Fructose. J Chem Ecol 17, 1529–1541 (1991). https://doi.org/10.1007/BF00984686
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DOI: https://doi.org/10.1007/BF00984686