Stereocontrolled Synthesis of Substituted Bicyclic Ethers through Oxy-Favorskii Rearrangement: Total Synthesis of (±)-Communiol E

The potential of the oxy-Favorskii rearrangement to form branched cis-fused bicyclic ethers was explored. Both tertiary and quaternary centers were constructed in highly stereospecific manners. Methanol and primary amines were effective nucleophiles for the rearrangement. The total synthesis of (+/-)-communiol E was achieved based on this method.