42 イリドイド配糖体の酸化順序とloganinのセコイリドイド配糖体への環開裂の機構

概要

論文の詳細を見る
The oxidative sequences shown in Scheme 1 were established by the incorporation of [10-^3H]-10-deoxygeniposidic acid (12) and [10-^3H]-geniposide (6) into asperuloside (8) in Daphniphyllum macropodum, [10^3H]-scandoside (9) into gardenoside (7) in Gardenia jasminoides and [10-^3H]-(6) into theviridoside (13) in Cerbera manghas. The results of the last experiment biosynthetically established the structure (13) of the glucoside proposed by Schmid. The incorporation of [10-^3H]-(9) into aucubin (10) in Aucuba japonica and [10-^3H]-(10) into catalposide (17) in Catalpa ovata was also established. Two mechanisms have been proposed for the cyclopentane ring cleavage of loganin (1) into the secoiridoid glucoside. One is the pathway via 10-oxyloganin (28) and the other is that through the Baeyer-Villiger type oxidation of 7-ketologanin (23) into 8-epikingiside (24). [7-^3H]-(1) was incorporated into morroniside (20) in Gentiana Thunbergii. [10-^3H]-7-Deoxyloganic acid (4), [10-^3H]-(1), [8-^3H]-(24), and [8-^3H]-kingiside (19) were all incorporated into jasminin (22) in Jasminum primulinum while [10-^<14>C]-sweroside (2) was not incorporated into the glucoside (22).
天然有機化合物討論会の論文
1970-10-01