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Synthesis of 3,9-Dialkyl-1,8-cineole Derivatives Based on Diels–Alder Adducts of Levoglucosenone with Isoprene and Butadiene

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Abstract

3,9-Dialkyl-substituted 1,8-cineole derivatives were synthesized by assembling the 2-oxabi­cyclo­[2.2.2]octane system on the basis of Diels–Alder adducts of levoglucosenone with isoprene and butadiene. Methylated adduct of levoglucosenone and isoprene showed a strong tendency to form 2-oxabicyclo[2.2.2]­octane system via intramolecular oxacyclization which readily occurred under conditions of double bond hydrogenation, attempted dehydration, and opening of the 1,6-anhydro bridge in the carbohydrate fragment, as well as by the action of electrophiles. Methylated adduct of levoglucosenone and butadiene underwent intra­molecular oxacyclization by the action of electrophiles. The presence of a methyl group in the cyclohexene ring of the adduct of levoglucosenone and isoprene forces the oxacyclization to selectively produce 1,5-epoxy derivative, whereas 1,4-epoxide is formed when such methyl group is absent. The use of methylene chloride as solvent increases the yield in the methylation of the keto group in the initial adducts with methylmagnesium iodide.

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ACKNOWLEDGMENTS

The authors thank Circa Group (Melbourne, Australia) for supplying commercial levoglucosenone. The spectral and analytical data were obtained using the facilities of the Chemistry joint center (Ufa Institute of Chemistry, Ufa Federal Research Center, Russian Academy of Sciences) and Agidel joint center (Ufa Federal Research Center, Russian Academy of Sciences).

Funding

This study was performed according to state assignment “Carbohydrates in the Synthesis of Chiral Carbo- and Heterocyclic Biologically Active Compounds.”

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Authors and Affiliations

  1. Ufa Institute of Chemistry, Ufa Federal Research Center, Russian Academy of Sciences, 450054, Ufa, Russia

    B. T. Sharipov, A. N. Davydova & F. A. Valeev

Authors
  1. B. T. Sharipov
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  2. A. N. Davydova
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  3. F. A. Valeev
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Correspondence to B. T. Sharipov.

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Translated from Zhurnal Organicheskoi Khimii, 2022, Vol. 58, No. 3, pp. 281–292 https://doi.org/10.31857/S0514749222030065.

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Sharipov, B.T., Davydova, A.N. & Valeev, F.A. Synthesis of 3,9-Dialkyl-1,8-cineole Derivatives Based on Diels–Alder Adducts of Levoglucosenone with Isoprene and Butadiene. Russ J Org Chem 58, 295–305 (2022). https://doi.org/10.1134/S107042802203006X

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