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

摘要

Structurally unique natural products pose biosynthetic puzzles whose solution can inspire new chemical reactions.Herein,we propose a unified biosynthetic pathway towards some complex meroterpe-noids-the hyperireflexolides,biyoulactones,hybea-nones 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 a-hydroxy-p-diketone rearrangement and an intramolecular aldol reaction to access four distinct natural product scaffolds from a common intermediate.