Chemical emulation of the biosynthesis of (±)-arnebidin

Abstract

We report a 13-step biomimetic total synthesis of (±)-arnebidin from 1,5-dihydroxynaphthalene. An intermolecular Diels–Alder homodimerization triggers spontaneous dehydrogenation and an intramolecular cycloaddition, delivering a single diastereomer under ambient conditions. This Diels–Alder cascade supports the proposed biosynthetic pathway and enables access to cyclopropane quinone dimers.