Highly stereoselective syntheses of the sex pheromone components of the southern green stink bug Nezara viridula (L.) and the green stink bug Acrosternum hilare (say)

Diastereoisomeric (Z)-(1R,2S,4S)- and (Z)-(1S,2R,4S)-epoxybisabolenes (1 and 2), sex pheromone components of the stink bugs Nezara viridula and Acrosternum hilare were synthesized stereoselectively in three steps from commercially available (-)-limonene oxide 3. Two other stereoisomers, (E)- (1R,2S,4S)- and (E)-(1S,2R,4S)-epoxybisabolenes (7 and 9) were obtained in two steps from the same starting material. The other four stereoisomers are also accessible by simply substituting (+)-limonene oxide for 3, providing short, stereoselective routes to all eight possible stereoisomers.