Asymmetric Divergent Synthesis of Miophytocen D, Roridin E, Verrucarin J, and Verrucarol

Herein, we report a divergent asymmetric synthesis of miophytocen D, roridin E, verrucarin J, and verrucarol. The synthesis features an exo-selective Diels–Alder cycloaddition, a biomimetic chemoselective oxacyclization for tetrahydropyran ring assembly, a conformation-controlled alkene–epoxy cyclization to access divergent molecular scaffolds, and a modular ring-closing metathesis (RCM)-based macrocyclization. This study delivers the first total synthesis of miophytocen D, furnishes hundred-milligram-scale access to verrucarol, and provides chemical support for the proposed biosynthetic transformation.