Total Synthesis of (±)-Periplanone B

Key words

(±)-periplanone B pheromone - anionic oxy–Cope rearrangement - Rubottom oxidation - Corey–Chaykovsky reaction - Sarett oxidation

Significance

(±)-Periplanone B is a sex pheromone produced by the female American cockroach, ­Periplaneta americana, to attract male cockroaches. In 1979, Still reported the first synthesis and determined its relative configuration. His elegant synthesis relied on an anionic oxy-Cope rearrangement to form the macrocyclic ten-membered ring. After subsequent Rubottom oxidation the stage was set to introduce the epoxide groups based on the principles of macrocyclic stereocontrol.

Comment

Divinylcyclohexenol E was obtained from enone A through a multi-step sequence. Ring expansion to cyclodecadienone F was achieved by anionic oxy-Cope rearrangement and further Rubottom oxidation. Bisepoxide J was obtained from enone G through nucleophilic epoxidation and Corey–Chaykovsky reaction. Deprotection and subsequent Sarett oxidation resulted in racemic periplanone B.