Diastereoselective intramolecular oxidopyrylium–alkene [5 + 2]-cycloaddition of substrates with a β-chiral center on alkene tethers: synthesis of 8-oxabicyclo-[3.2.1]-octenone heterocycles

We investigated the asymmetric intramolecular oxidopyrylium–alkene [5 + 2]-cycloaddition reaction of substrates bearing tethered alkenes containing β-chiral centers. The effect on the cycloadduct diastereoselectivity was examined for carbon chain tethered alkenes or alkoxy tethered alkenes with varying chain lengths that can form 5-, 6- and 7-membered rings. We also probed the effect of varying steric bulk on the β-chiral center substituents on cycloadduct diastereoselectivity. Various substrates with carbon chain tethered alkenes were synthesized using the Lewis acid mediated conjugate addition of an allyl group to furanyl enones. Reduction of the resulting ketones followed by the Achmatowicz reaction of furanyl alcohol provided oxidopyrylium–alkene substrates. The asymmetric [5 + 2]-cycloaddition proceeded with high diastereoselectivity for cycloadducts with five and six-membered rings. However, cycloadducts with a seven-membered ring showed no diastereoselectivity. Stereochemical models are provided to explain the high diastereoselectivity for five and six-membered products.

• Publication year

  2025

• Venue

  Organic and biomolecular chemistry

• Publication date

  2025-11-12

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1039/d5ob01429hPMID 41222563PMCID 12609155
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

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