Intramolecular Tricarbonyl-Ene Reactions and α-Hydroxy-β-Diketone Rearrangements Inspired by the Biosynthesis of Polycyclic Polyprenylated Acylphloroglucinols.

ABSTRACT: Structurally unique natural products pose biosynthetic puzzles whose solution can inspire new chemical reactions. Herein, we propose a unified biosynthetic pathway towards some complex meroterpenoids-the hyperireflexolides, biyoulactones, hybeanones and hypermonones. This hypothesis led to the discovery of uncatalyzed, intramolecular carbonyl-ene reactions that are spontaneous at room temperature. We also developed an anionic cascade reaction featuring an α-hydroxy-β-diketone rearrangement and an intramolecular aldol reaction to access four distinct natural product scaffolds from a common intermediate.

SUBMITTER: Zur Bonsen AB 

PROVIDER: S-EPMC9541541 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature