Stereochemistry of olefinic bond formation in defensive steroids of Acilius sulcatus (Dytiscidae).

The defensive secretion of Acilius sulcatus contains a number of pregnane derivates: cortexone, 20alpha-hydroxy-4-pregnen-3-one, together with the unusual delta4,6 dienes, 6,7-dehydrocortexone, 20alpha-hydroxy-4,6-pregnadien-3-one and 4,6-pregnadien-3,20-dione. The synthesis of all these steroids except cortexone is described. Complete separation of the steroids of Acilius can be achieved by high-performance liquid chromatography on the reversed-phase column system. During biosynthesis of the Acilius steroids from cholesterol, introduction of the delta4 and delta6 bonds involves elimination of the 4beta and 7beta hydrogens, respectively. Possible mechanisms of formation of the delta4,6 steroids are discussed.