Reiterative Synthesis of <i>trans</i>‐Fused Polytetrahydropyrans Using the Oxiranyl Anion

Abstract

Abstract The oxiranyl anion is a very unstable nucleophilic epoxide. This previously uncommon nucleophile has now been used for the synthesis of polycyclic ethers. Alkylation of an oxiranyl anion, a three‐carbon building block, with a triflate derived from tetrahydropyran‐methanol followed by acid‐catalyzed 6‐ endo cyclization provides a trans ‐fused bicyclic compound. Reiterative application of this procedure enables the rapid construction of trans ‐fused polytetrahydropyrans.