Synthesis of β-aryl-γ-lactones and relationship: Structure – antifeedant and antifungal activity

Abstract

Eighteen racemic β-aryl-γ -lactones derived from simple aromatic aldehydes have been obtained in the chemical synthesis. Iodolactones (5c and 6c) were synthesized from (E)-4-(benzo [d][1 ,3 ]-dioxol-5 -yl)-but-3-en-2-one (1). Reductive dehalogenation of iodolactones 5a-c and 6a-c afforded γ -ethyl-γ -lactones (7a-c, 8a-c) whereas the unsaturated lactones (9a-c, 10a-c) were obtained by dehydrohalogenation of iodolactones. All synthesized lactones were fully characterized by spectroscopic data (NMR, IR, HRMS) and subjected to the tests on the antifeedant activity towards Tribolium confusum, Trogoderma granarium and Sitophilus granaries as well to the tests on the antifungal activity towards four Fusarium species. The biological tests allowed to find some relationships between the structure and biological activity of the compounds studied. γ -Ethyl-γ -lactones 7a-c, 8a-c and unsaturated lactones 9a-c, 10a-c were usually stronger antifeedants than their parent iodolactones 5a-c and 6a-c. trans-Iodolactones 6a-c were more active than cis isomers 5a-c both in antifeedant and antifungal assays. The structure of aromatic substituent was the key factor in antifungal activity. The lactones with benzo [d][1,3]dioxole ring (5c, 6c, 7c, 8c, 9c) were the most active whereas those with unsubstituted benzene ring exhibited almost no activity.

Kinetic resolution of (E)-4-(2′,5′-dimethylphenyl)-but-3-en-2-ol and (E)-4-(benzo[d][1′,3′]dioxol-5′-yl)-but-3-en-2-ol through lipase-catalyzed transesterification

“…This alcohol was obtained earlier by Skrobiszewski et al as a starting material in the synthesis of racemic hydroxylactones with antifeedant activity. 31 Alcohols 5 and 6 were also treated with acetyl chloride and propionyl chloride to afford racemic acetates 7a,8a and propionates 7b,8b (Scheme 1), not reported previously, which were necessary as the standards for chiral gas chromatography.…”

“…31 36À38°C); spectroscopic data consistent with those reported in the literature. 31 4.5. General procedure for the synthesis of racemic acetates 7a,8a and propionates 7b,8b…”

Synthesis, Characterization, Cytotoxicity, and Antibacterial Properties of trans‐γ‐Halo‐δ‐lactones

“…Sensory properties make them useful in the production of cosmetics and in the food industry,w here they are responsible for the smell and taste of many products. [21] An important property of lactones is the deterrent ac-tivity, [22][23][24][25][26][27] which can be utilized in the productiono fi nsectcontrol agents.…”

W(OTf)6‐Catalyzed Synthesis of γ‐Lactones by Ring Contraction of Macrolides or Ring Closing of Terminal Hydroxyfatty Acids in Ionic Liquid

“…Also catalyzed by metal triflates [Hf(OTf) 4 in this case],C ollins and co-workersr eported efficient direct macrolactonization of seco acids in high yield without hydrolysis, even in the presence of excess water,f orming av ariety of macrolactones and benzolactones( 55-90 %). [12] The ring of macrolides is contracted when Lewis acidic metal triflates are used as catalysts. [1b] Previousr eports have verified that metal triflates are efficient catalysts for the ring-opening and polymerization of lactones, [10] and our earlier research involved ring-opening poly-merization,r ing-closing depolymerization, and ring contraction by rearrangemento fl actones in the presence of W(OTf) 6 ,a lbeit without as ystematic study.…”

“…[3b] Macrolidesa re mainly secondary metabolites of bacteria and fungi, whicha re abundant in nature. [12] The ring of macrolides is contracted when Lewis acidic metal triflates are used as catalysts. Further expansion of the substrate scope to include terminal hydroxyfatty acids affords ag reen,s imple, and highly atom-economical method to synthesize g-lactones was developed with the ionic liquid [EMIM]OTf as the solvent.…”