Chemoenzymatic Synthesis of 13-Oxoverruculogen.

Verruculogens are rare fumitremorgin alkaloids that contain a highly unusual eight-membered endoperoxide. In this paper, we report a concise chemoenzymatic synthesis of 13-oxoverruculogen using enzymatic C-H peroxidation and rhodium-catalyzed C-C bond activation reactions to install the eight-membered endoperoxide and the pentacyclic core of the natural product, respectively. Our strategy involves the use of 13--fumitremorgin B as a substrate analog for endoperoxidation by verruculogen synthase, FtmOx1.