23 α-SantoninからGermacrane型化合物への変換 : Dihidrocostunolideの合成

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概要

• 論文の詳細を見る

• We describe a novel method for the preparation of cyclodecanone intermediate(29, 30, 31, 33) which is useful for the synthesis of not only germacrene-type sesquiterpenoids but guaiane-type sesquiterpenoids, and also describe the synthesis of dihydrocostunolide(42) isolated from cotus root oil. α-Santonin was treated with m-chloroperbenzoic acid to give the α-epoxide(2), β-epoxide(3) and diepoxide(4). Selective reduction of the carbonyl group of 2 with LiAlH_4 afforded a mixture of 5 and 6. Similar reduction of 3 gave a mixture of 7 and 8. The allyl alcohols(5, 6, 7, 8) were stereospecifically chlorinated to the corresponding 3-chloro derivatives(9, 10, 11, 12) having the inverted configuration of C_3-H by the action of MsCl(or TsCl)-pyridine. A diastereomeric mixture of the chloride(9, 10) was treated with NaI-Zn to give a dienol (23), while treatment of a mixture of 11 and 12 gave a dienol(24). The irradiation of 23 (7W low- pressure mercury lamp, MeOH, 15℃) provided a diastereomeric mixture of dienones(29, 30, 31). Treatment of 29 with refluxing benzene or SiO_2 gave a guaianolide-type derivative(32) in quantitative yield. Hydrogenation of 29 over Pd-C, followed by treatment of the resulting dihydro derivative(37) with NaBH_4 afforded an alcohol(40). 40 was converted into a mesylate(41) which was then treated with tetra-n-butylammonium oxalate to give the dihydrocostunolide. The synthetic dihydrocostunolide was identical with an authentic specimen in tlc, glpc, ms, it and nmr spectra.

• 天然有機化合物討論会の論文
• 1976-09-20

著者

• 辰野 高司

  理化学研究所

• 藤本 康雄

  The Institute Of Physical And Chemical Research

• 辰野 高司

  Institute of Physical and Chemical Research

• 藤本 康雄

  理研

• 辰野 高司

  理研

• 清水 猛

  理研

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