26 酒石酸を不斉源とする(+)-アスペルリンの全合成(口頭発表の部)

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概要

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• (+)-Asperlin (3) of antibiotic and antitumor activities is recognized structurally as the most fundamental and smallest representative of biologically active 5-oxygenated 5,6-dihydro-2-pyrones with the oxygen-functionalized sidechain at the 6-position. We have developed a short-step transformation of tartaric acid (6) as a chiral source effectively utilizing the C_2 symmetry to optically active 6,8-dioxabicyclo[3.2.1]octane derivative (14) inaccessible from common 6-carbon sugars, and applied the method to natural product synthesis. Now we report a stereoselective total synthesis of (3) starting from (S,S)-tartaric acid (6) featuring regioselective olefination of the bicyclic system (14), the method of which was utilized to a short-step synthesis of optically active 7-exoethyl-5-methyl-6,8-dioxabicyclo[3.2.1]oct-3-ene (8), one of the components of the pheromone of the male house mouse Mus musculus, and regio- and stereoselective introdduction of the chiral oxygen functionalities at the C(2)- and C(7')-positions of the bicyclic olefin (16) (the latent 5- and 8-positions of 3, respectively) under favor of the architecture of 16. Furthermore, a mild and efficient method for construction of unstable oxygenated 5,6-dihydro-2-pyrone skeleton through partial ring opening of the bicyclic system providing a pyranoid (25) followed by MnO_2-oxidation of unsaturated cyclic hemiacetal (30) was developed. The strategy described is believed to be potential for wide applicability to syntheses of biologically important oxygenated 6-substituted-2-pyrones.

• 天然有機化合物討論会の論文
• 1992-09-10

著者

• 正木 幸雄

  Gifu Pharmaceutical University

• 正木 幸雄

  岐阜薬科大学:(現)名城大学薬学部薬化学教室

• 伊藤 彰近

  岐阜薬大

• 正木 幸雄

  岐阜薬大

• 小田 博久

  Gifu Pharmaceutical University

• 今枝 稔博

  Gifu Pharmaceutical University

• 伊藤 彰近

  岐阜薬科大学創薬化学大講座合成薬品製造学研究室

• 伊藤 彰近

  岐阜薬科大学

• 今枝 稔博

  岐阜薬大

• 小田 博久

  岐阜薬大

• 正木 幸雄

  岐阜薬科大学

• Oda Hirohisa

  Gifu Pharmaceutical University

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