Stereoselective deprotonation installs an unusual Z-8,9 double bond during biosynthesis of the diterpene pheromone sobralene

Abstract

A terpene synthase from the sandfly Lutzomyia longipalpis, catalyses stereoselective removal of the pro-S proton from C8 of geranylgeranyl diphosphate to generate the characteristic (Z)-8,9 double bond seen in the diterpene pheromone sobralene. Retention of deuterium in structurally related minor products demonstrates that they are not produced via sobralene, but are made directly by the enzyme.