title: Alternative synthesis of the Colorado potato beetle pheromone.
abstract: A concise preparation of the pheromone secreted by the male Colorado potato beetle [viz. (3S)-1,3-dihydroxy-3,7-dimethyl-6-octen-2-one] was accomplished in four steps starting from 2-fluoronerol or 2-fluorogeraniol. The key step in the synthesis involves a 6-endo epoxide ring-opening with ester participation that simultaneously inverts the 3R-configuration of the (3R)-2,3-epoxy-2-fluoroprenyl acetate intermediate and installs the ketone functionality of the semiochemical. Extensive NMR studies validate the proposed 6-endo mechanism of the featured rearrangement, which under anhydrous conditions resulted in the formation of two bicyclic 1,3-dioxan-5-ones via an unprecedented intramolecular Prins cyclization.
authors.affiliation: Department of Chemistry, University of Illinois , Urbana-Champaign, Illinois 61801, United States.
authors.forename: Juan A
authors.initials: JA
authors.lastname: Faraldos
authors.forename: Robert M
authors.initials: RM
authors.lastname: Coates
authors.forename: José-Luis
authors.initials: JL
authors.lastname: Giner
mesh_terms: D000818:Animals; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D001517:Coleoptera; D003120:Colorado; D003500:Cyclization; D004146:Dioxanes / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008297:Male; D015394:Molecular Structure; D010675:Pheromones / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D001643:Bridged Bicyclo Compounds; D004146:Dioxanes; D010675:Pheromones
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