Biosynthesis of algal pheromones. A model study with the composite Senecio isatideus.
Several cyclic and alicyclic C11 hydrocarbons have been shown to act as gamete releasing and/or attracting pheromones during sexual reproduction of brown algae (Phaeophyceae). The same compounds are also found in the essential oils of various plants, of which the occurrence of the cycloheptadiene-pheromone ectocarpene in Senecio isatideus (Compositae) is noteworthy. Administration of [3H]dodeca-3,6,9-trienoic acid to cuttings of this plant leads to incorporation of radioactivity into ectocarpene. Double-bond-deuterated nona-3,6-dienoic acid is converted to fucoserratene, the pheromone of several Fucales, which is certainly not present among the hydrocarbons of Senecio. This proves that the pool of medium-chain, multiply unsaturated fatty acids includes precursors of all types of highly unsaturated hydrocarbons. Appropriately labelled (deuterium markers) fatty acid homologues were synthesized and applied to Senecio plantlets to unravel the mechanistic aspects. The results strongly suggest radical initiation of the pheromone biosynthesis by abstraction of a single hydrogen from a 1,4-pentadienyl segment of the fatty acid followed by oxidation to the corresponding cation. This causes fragmentation of the reactive intermediate into an olefine and carbon dioxide by neighbouring-group participation of the flanking double bonds. A tentative biosynthetic scheme is deduced from the experimental results which also sets the stereochemistry of the algal pheromones into a uniform mechanistic concept.
D000818:Animals; D055598:Chemical Phenomena; D002621:Chemistry; D002849:Chromatography, Gas; D003508:Cycloheptanes / Q000096:biosynthesis; D003903:Deuterium; D056890:Eukaryota / Q000378:metabolism*; D005227:Fatty Acids / Q000378:metabolism; D006838:Hydrocarbons / Q000032:analysis; D050356:Lipid Metabolism; D013058:Mass Spectrometry; D000459:Phaeophyceae / Q000378:metabolism*; D010675:Pheromones / Q000096:biosynthesis*; D010947:Plants, Toxic; D012674:Senecio / Q000378:metabolism*
D003508:Cycloheptanes; D005227:Fatty Acids; D006838:Hydrocarbons; D010675:Pheromones; C044377:ectocarpene; D003903:Deuterium