Determination of the absolute configuration of the male aggregation pheromone, 2-methyl-6-(4′-methylenebicyclo[3.1.0]hexyl)hept-2-en-1-ol, of the stink bug Erysarcoris lewisi (Distant) as 2Z,6R,1′S,5′S by its synthesis

Abstract Lipase-catalyzed asymmetric acetylation of a mixture of (6 R ,1′ S ,4′ S ,5′ R )- and (6 R ,1′ R ,4′ R ,5′ S )-7′-norsesquisabinen-4′-ol ( 3 ) afforded a separable mixture of the recovered former and the acetate of the latter. The recovered alcohol was oxidized to (6 R ,1′ S ,5′ R )-sesquisabina ketone ( 2 ), whose absolute configuration could be assigned by its CD comparison with (1 R ,5 S )-sabina ketone ( 4 ). Conversion of (6 R ,1′ S ,5′ R )-sesquisabina ketone ( 2 ) to the bioactive pheromone revealed the stereostructure of the male aggregation pheromone of the stink bug Erysarcoris lewisi (Distant) to be (2 Z ,6 R ,1′ S ,5′ S )-2-methyl-6-(4′-methylenebicyclo[3.1.0]hexyl)hept-2-en-1-ol (sesquisabinen-1-ol, 1 ).