Gold-catalyzed endo-selective Ring-opening of Epoxides and its Application in Construction of Poly-ethers

Tetrahydropyran and oxepane scaffolds are found in many classes of natural products and medicinally relevant small molecules. Here we describe a gold-catalyzed 6-endo selective ring-opening of epoxides that provides rapid access to subunits of marine ladder-like poly-ethers (MLP), emulating the Nakanishi’s hypothesis on the biosynthesis of these toxins. The synthetic utility of this method is also demonstrated in the preparation of the tricyclic core of tetrahydropyran-containing macrolide natural products lituarines A–C.