Preuisolactone A is a recently isolated, racemic natural product from the endophytic fungus <i>Preussia isomera</i>. It is marked by a caged structure that contains seven adjacent stereocenters, two of which are quarternary. Biosynthetically, preuisolactone A was proposed to be formed via the terpene pathway featuring several oxidative editing steps. We propose an alternative biosynthetic hypothesis and have completed a short, biomimetic synthesis that follows our proposal. Its features are a purpurogallin-type [5+2]-cycloaddition, followed by a retro-Dieckmann reaction, vinylogous aldol addition, oxidative lactonization and a final, unprecedented benzilic acid rearrangement. The synthesis furnished preuisolactone A in essentially three steps in high overall yield. Our work explains why preuisolactone A has been isolated as a racemate and suggests that it is not a terpenoid but a phenolic polyketide.

Elucidating the origin of preuisolactone A via biomimetic synthesis

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.