Studies on Terpenoids and Related Alicyclic Compounds. XVII. Total Syntheses of Sesquiterpenoids ; (±)-Isopetasol, (±)-3-Epiisopetasol, (±)-Warburgiadione, and (±)-Petasitol

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概要

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• The total syntheses of (±)-isopetasol (24), (±)-3-epiisopetasol (17), (±)-warburgiadione (23), (±)-petasitol (27a) are described. A key intermediate (11) was synthesized by the Robinson annulation of 2,3-dimethylcyclohexane-1,4-dione (6), which was prepared starting from 2,3-dimethylphenol (2) and methyl vinyl ketone via intermediates 8 and 9. Reduction of 11 with NaBH_4 gave epimeric alcohols (13a and 14a) in the 7 : 3 ratio. Stereochemistry of 13a and 14a and the coresponding acetates (13b and 14b) were confirmed by NMR spectrometry. Introduction of the C-7 side chain in 13a was made with CH_3Li to give 16 which was treated with HCl-MeOH to afford (±)-17. While, the same procedure applied to 14a was unsucessful. Ketal (19) derived from 11 was converted to isopropyl alcohol (21) by two routes. Treatment of 21 with HCL-MeOH gave (±)-isopetasone (22). (±)-23 and (±)-24 were obtained from 22 by dehydrogenation and reduction, respectively. Dehydrogenation of 21 by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) gave a cross dienone (25). Deketalization of 25 followed by reduction afforded (±)-27a and (±)-3-epipetasitol (28).

• 社団法人日本薬学会の論文
• 1979-02-25

著者

• 佐藤 毅

  東京理科大学理学部

• 佐藤 毅

  Faculty of Pharmaceutical Sciences, Science University of Tokyo

• 山川 浩司

  Faculty of Pharmaceutical Sciences, Science University of Tokyo

• 山川 浩司

  Faculty Of Pharmaceutical Sciences Science University Of Tokyo

• 坂口 礼司

  Faculty of Pharmaceutical Sciences, Science University of Tokyo

• 坂口 礼司

  Faculty Of Pharmaceutical Sciences Science University Of Tokyo

• 坂口 礼司

  Faculty Of Pharmaceutical Sciences School Of Medicine Hokkaido University

• 伊豆田 格

  Faculty of Pharmaceutical Sciences, Science University of Tokyo

• 岡 弘

  Faculty of Pharmaceutical Sciences, Science University of Tokyo

• 小林 雅人

  Faculty of Pharmaceutical Sciences, Science University of Tokyo

• 岡 弘

  Faculty Of Pharmaceutical Sciences Science University Of Tokyo

• 小林 雅人

  Faculty Of Pharmaceutical Sciences Hoshi University

• 山川 浩司

  東京理大

• 伊豆田 格

  Faculty Of Pharmaceutical Sciences Science University Of Tokyo

• Satoh T

  Department Of Applied Chemistry Faculty Of Engineering Osaka University

• Sato Toshiyuki

  Yamagata Research Institute Of Technology

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