title: Oxidative carbon-carbon bond cleavage is a key step in spiroacetal biosynthesis in the fruit fly Bactrocera cacuminata.
abstract: The early steps of spiroacetal biosynthesis in the fruit fly Bactrocera cacuminata (Solanum fly) have been investigated using a series of deuterium-labeled, oxygenated fatty acid like compounds. These potential spiroacetal precursors were administered to male flies, and their volatile emissions were analyzed for specific deuterium incorporation by GC/MS. This has allowed the order of early oxidative events in the biosynthetic pathway to be determined. Together with the already well-established later steps, the results of these in vivo investigations have allowed essentially the complete delineation of the spiroacetal biosynthetic pathway, beginning from products of primary metabolism. A fatty acid equivalent undergoes a series of enzyme-mediated oxidations leading to a trioxygenated fatty acid like species that includes a vicinal diol. This moiety then undergoes enzyme-mediated oxidative carbon-carbon bond cleavage as the key step to generate the C9 unit of the final spiroacetal. This is the first time such an oxidative transformation has been reported in insects. A final hydroxylation step is followed by spontaneous spiro-cyclization. This distinct pathway adds further to the complexity and diversity of biosynthetic pathways to spiroacetals.
authors.affiliation: School of Chemistry and Molecular Biosciences, University of Queensland , Brisbane 4072, Australia.
authors.forename: Arti A
authors.initials: AA
authors.lastname: Singh
authors.forename: Jessica A
authors.initials: JA
authors.lastname: Rowley
authors.forename: Brett D
authors.initials: BD
authors.lastname: Schwartz
authors.forename: William
authors.initials: W
authors.lastname: Kitching
authors.forename: James J
authors.initials: JJ
authors.lastname: De Voss
mesh_terms: D000080:Acetals / Q000138:chemical synthesis* / Q000737:chemistry*; D000818:Animals; D053898:Biosynthetic Pathways; D002244:Carbon / Q000737:chemistry*; D008401:Gas Chromatography-Mass Spectrometry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013141:Spiro Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D033621:Tephritidae / Q000737:chemistry / Q000378:metabolism*
chemical_list: D000080:Acetals; D013141:Spiro Compounds; D002244:Carbon