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.
Keywords: Biomimetic Synthesis; Carbonyl-Ene Reaction; Cascade Reactions; Natural Products; Rearrangement.
© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.