Biomimetic Synthesis of Hitorins A and B via an Intermolecular Alkoxy Radical-Olefin Coupling Cascade

A biomimetic synthesis of hitorins A and B was achieved based on our modified biosynthetic proposal. In our synthesis, a radical cascade reaction between an alkoxy radical, generated from a hydroperoxide, and a monoterpene (+)-sabinene renders the tetrahydrofuran ring of hitorins A and B. In addition, experimental results supported that the oxidative cleavage of the tetrasubstituted olefin in a key intermediate is via a radical oxidation cascade followed by a Grob fragmentation.