Intramolecular Tricarbonyl-Ene Reactions and alpha-Hydroxy-beta-Diketone Rearrangements Inspired by the Biosynthesis of Polycyclic Polyprenylated Acylphloroglucinols

Version of record online: July 14, 2022Structurally 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.Andreas B. zur Bonsen, Ricardo A. Peralta, Thoma sFallon, David M. Huang, and Jonathan H. Georg