Still WC.
* Columbia University, New York, USA
(±)-Periplanone-B. Total Synthesis and Structure of the Sex Excitant Pheromone of the American Cockroach.
J. Am. Chem. Soc. 1979;
101: 2493-2495
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.
