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Molecular Iodine as an Optimal Catalyst of Alkene Migration in Sesquiterpene Lactones to a Hindered endo-Position

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Abstract

Trifluoroacetic acid has induced the migration of the Δ4,14 exo-double bond of isoalantolactone to the endo-position (Δ4) with the formation of alloalantolactone. Different conditions theoretically leading to the conversion of isoalantolactone into its synthetically less accessible isomer with a double bond in position Δ3 (sulfuric acid, perchloric acid, formic acid, microwave irradiation of the lactone adsorbed on various carriers) have been screened. Refluxing of isoalantolactone with iodine has led to rapid conversion with predominant formation of lactone isomers with a double bond in positions Δ3 and Δ4 in approximately equal yield. Molecular iodine has also turned out to be the optimal agent for the isomerization of dehydrocostus lactone.

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Funding

This study was financially supported by the Ministry of Science and Higher Education of the Russian Federation in the scope of the State Task to the Institute of Physiologically Active Substances, Russian Academy of Sciences (topic no. FFSN-2021-0013, 2021–2023).

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Authors and Affiliations

  1. Institute of Physiologically Active Substances, Russian Academy of Sciences, 142432, Chernogolovka, Russia

    A. V. Semakov

  2. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991, Moscow, Russia

    V. K. Brel

Authors
  1. A. V. Semakov
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  2. V. K. Brel
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Correspondence to A. V. Semakov.

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V.K. Brel is a member of the Editorial Board of the Russian Journal of General Chemistry. Other authors declare that they have no conflicts of interest.

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Semakov, A.V., Brel, V.K. Molecular Iodine as an Optimal Catalyst of Alkene Migration in Sesquiterpene Lactones to a Hindered endo-Position. Russ J Gen Chem 92, 1392–1400 (2022). https://doi.org/10.1134/S1070363222080059

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