55 5-8-5-員三環性テルペノイド及び関連化合物の合成 : ソルダリシン骨格の生合成的合成(口頭発表の部)

概要

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In our first total synthesis of cycloaraneosene (1), the structure of its hydroxyderivative has been reviced from 9α-(12) to 8β-hydroxycycloaraneosene (4) by physical data comparisons of synthetic 12 with the natural substance. To obtain a concrete proof for this conclusion, both stereoisomers of 8-hydroxycycloaraneosene have been synthesized via an improved 8-membered ring formation, a Lewis acid-catalized intramolecular enereaction, and a [2,3]-rearrangement of an allylselenoxido derivative. The 4 and 19, thus obtained, were identical with natural hydroxycycloaraneosene and its epimer, respectively. The stereochemistries of the hydroxyls of these compounds were deduced as had been expected by a differential NOE experiment on compound 4. The framework of Sordaricin (5), which is believed to be biosynthesized from 1 via 4, has been constructed by an intramolecular Diels-Alder reaction of a B-seco-derivative of 1.
天然有機化合物討論会の論文
1988-09-26