title: Alkyl-Substituted δ-Lactones Derived from Dihydrojasmone and Their Stereoselective Fungi-Mediated Conversion: Production of New Antifeedant Agents.
abstract: A chemoenzymatic method was applied to obtain optically pure alkyl-substituted δ-lactones. First, chemical Baeyer-Villiger oxidation of dihydrojasmone (1) was carried out, affording two new alkyl-substituted δ-lactones: 3,4-dihydro-5-methyl-6-pentyl-2H-pyran-2-one (2) and 5-methyl-6-pentyl-1,13-dioxabicyclo[4.1.0]heptan-2-one (3). In the next step, fungal strains were investigated as biocatalysts to enantioselective conversion of δ-lactones (2) and (3). The fungal cultures: Fusarium culmorum AM10, Fusarium equiseti AM15 and Beauveria bassiana AM278 catalyzed the stereoselective hydration of the double bond of lactone (2) (ee = 20%-99%) while Didymosphaeria igniaria KCh6670 proved to be the best biocatalyst for the reduction of carbonyl group in the epoxylactone (3) (ee = 99%). In both cases, chiral oxyderivatives were obtained in low to high yields (7%-91%). The synthetic lactones (2), (3) and its derivatives (4), (5) were tested for their antifeedant activity towards larvae and adults of lesser mealworm (Alphitobius diaperinus Panzer) and peach potato aphid (Myzus persicae [Sulzer]) and some of them were active towards studied insects.
authors.affiliation: Department of Chemistry, Wroclaw University of Environmental and Life Sciences, Norwida 25, Wrocław 50-375, Poland. anna.gliszczynska@wp.pl.
authors.forename: Anna
authors.initials: A
authors.lastname: Gliszczyńska
authors.affiliation: Bioprocess and Biomedical Engineering Division, Wroclaw University of Technology, Norwida 4/6, Wrocław 50-373, Poland. damiansmb@gmail.com.
authors.forename: Damian
authors.initials: D
authors.lastname: Semba
authors.affiliation: Department of Invertebrate Zoology, Nicolaus Copernicus University, Lwowska 1, Toruń 87-100, Poland. mszczep@umk.pl.
authors.forename: Maryla
authors.initials: M
authors.lastname: Szczepanik
authors.affiliation: Department of Botany and Ecology, University of Zielona Góra, Szafrana 1, Zielona Góra 65-516, Poland. k.dancewicz@wnb.uz.zgora.pl.
authors.forename: Katarzyna
authors.initials: K
authors.lastname: Dancewicz
authors.affiliation: Department of Botany and Ecology, University of Zielona Góra, Szafrana 1, Zielona Góra 65-516, Poland. b.gabrys@wnb.uz.zgora.pl.
authors.forename: Beata
authors.initials: B
authors.lastname: Gabryś
mesh_terms: D000818:Animals; D001042:Aphids; D052982:Beauveria / Q000378:metabolism*; D061046:Biological Control Agents / Q000737:chemistry / Q000378:metabolism / Q000494:pharmacology; D003517:Cyclopentanes / Q000737:chemistry / Q000378:metabolism / Q000494:pharmacology; D005670:Fusarium / Q000378:metabolism*; D007783:Lactones / Q000737:chemistry / Q000378:metabolism / Q000494:pharmacology; D054883:Oxylipins / Q000737:chemistry / Q000378:metabolism / Q000494:pharmacology; D013712:Tenebrio
chemical_list: D061046:Biological Control Agents; D003517:Cyclopentanes; D007783:Lactones; D054883:Oxylipins; C086299:jasmone
keywords: Baeyer–Villiger oxidation; alkyl-substituted δ-lactones; dihydrojasmone; oxyfunctionalization