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Novel Syntheses of Isomers of Damascenone from Ethyl 2,6,6-Trimethyl-4-oxo-2-cyclohexene-1-carboxylate

  • Lee, Woo-Young (Department of Chemistry, Seoul National University) ;
  • Jang, Se-Young (Department of Chemistry, Seoul National University) ;
  • Lee, Jun-Gu (Department of Chemistry, Seoul National University) ;
  • Chae, Woo-Ki (Department of Chemistry Education, Seoul National University)
  • Published : 1991.02.20

Abstract

Three isomers of damascenone, odorous terpenic ketones, have been synthesized conveniently from a same starting material, ethyl 2,6,6-trimethyl-4-oxo-2-cyclohexene-1-carboxylate(1), which was easily available by the acid-catalyzed condensation of mesityl oxide or acetone with ethyl acetoacetate. ${\alpha}$-Damascenone(7) was prepared by converting the enone ester 1 into the corresponding tosylhydrazone(4), followed by treating with 4 molar equiv of allyllithium. ${\beta}$-Damascenone(12) was synthesized by chemoselective reduction of 1 with sodium borohydride/cerium chloride to give corresponding allylic alcohol 8, conversion of 8 into acetate 9, and thermal decomposition of 9 with DBU to afford ethyl ${\beta}$-safranate(10), followed by reaction with an excess amount of allyllithium. ${\gamma}$-Damascenone(15) was obtained by dehydration of 8 with boric acid to furnish ${\gamma}$-safranate(13), followed by treatment with 2 molar equiv of allyllithium.

Keywords

References

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  2. New Preparation Methods for α-Damascone, &ggr;-Damascone, and &bgr;-Damascenone using Pyronenes vol.37, pp.15, 1991, https://doi.org/10.1080/00397910701462898
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