Secondary plant metabolites as defence against herbivores and oxidative stress : Synthesis, isolation and biological evaluation

Abstract: In this thesis the isolation, synthesis and biological evaluation of natural defense compounds against herbivores or oxidative stress is discussed.The first part concerns the metabolites of platyphylloside ((5S)-5-hydroxy-1,7-bis-(4-hydroxyphenyl)-3-heptanone-5-O-β-D-glucopyranoside), a phenolic glucoside found in birch (Betula pendula) that possess digestibility inhibiting activity in herbivores. The structure-activity relationship of platyphylloside analogues were investigated regarding to stereochemistry and substitution pattern on the aromatic rings. The metabolites formed in vitro in rumen fluid were synthesized and the active metabolite determined as (R)-centrolobol (1,7-bis-(4-hydroxyphenyl)-3-heptanol). Treatment of mice and rats with rac-centrolobol did not effect either food intake or body weight. Effect of platyphylloside in moose was also investigated, and the results indicate that there was an in vivo digestibility reducing activity.The second part concerns naturally occurring antioxidants. Avenanthramides is a class of phenolic antioxidants found in oat (Avena sativa). Avenanthramides derived from either anthranilic acid or 5-hydroxyanthranilic acid were evaluated for their antioxidative capacity and quantified in oat extracts. Avenanthramides derived from 5-hydroxyanthranilic acid possessed higher activity than those from anthranilic acid. The order of reactivity depending on substitution pattern on the phenolic moiety was found to be 4-hydroxy < 4-hydroxy-3-methoxy < 3,5-dimethoxy-4-hydroxy and 3,4-dihydroxy. A synthesis towards antioxidative compounds such as 4-deoxycarbazomycin was developed.The third part concerns the isolation of compounds from Lodgepole pine (Pinus contorta) with antifeedant activity against pine weevil (Hylobius abietis). Two compounds possessing high activity were isolated and identified.