45 Tricyclo[3.3.0.0^<2,8>]octan-3-one化合物を鍵中間体とするポリキナン型セスキテルペン類の合成研究 : (±)-Pentalenene及び(±)-Quadroneの全合成

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概要

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• Synthesis of (±)-pentalenene (3), (±)-descarboxyquadrone (4), and (±)-quadrone (5) has been achieved via regioselective C-C bond cleavages of the cyclopropane ring on tricyclo[3.3.0.0^<2,8>]octan-3-one derivatives (2a-2d) which were easily obtained from the cyclopentenone (1). 1. Total Synthesis of (±)-Pentalenene (3) The Birch reduction of 2a resulted in an exclusive C_2-C_8 bond cleavage to give 16, which was transformed into the triquinane (20) by a several-step sequence. Treatment of 20 with methyllithium and subsequent with p-TsOH afforded (±)-pentalenene (3) along with its diastereoisomer (24). 2. Total Synthesis of (±)-Descarboxyquadrone (4) Reaction of 2b with HCOOH-H_2SO_4 and then the alkaline hydrolysis yielded the C_1-C_2 bond cleaved product (27: X=OH) mainly. Furthermore, the exclusive C_1-C_2 bond cleavage was accomplished by an intramolecular participation of a carboxyl group. Namely, treatment of the carboxylic acid (2c) with p-TsOH gave the desired product (29) as a sole product. Each of 27 and 29 was able to be converted into the diketone (36), which was transformed into (±)-descarboxy-quadrone (4) via 40. 3. Formal Total Synthesis of (±)-Quadrone (5) The carboxylic acid (2d), easily obtained from 2b via a C-1 unit introduction at C_3, was exposed to p-TsOH to afford 30. By a several-step sequence, 30 was converted into 46, which had been transformed into (±)-quadrone (5) by S. Danishefsky.

• 天然有機化合物討論会の論文
• 1986-09-09

著者

• 今西 武

  Faculty Of Pharmaceutical Sciences Osaka University

• 岩田 宙造

  阪大・薬

• 今西 武

  阪大・薬

• 岩田 宙造

  大阪大学薬学部製薬化学科

• 松井 宗隆

  Faculty of Pharmaceutical Sciences, Osaka University

• 松井 宗隆

  阪大・薬

• 仁張 総子

  阪大・薬

• 山下 正行

  阪大・薬

• 山下 正行

  Faculty Of Pharmaceutical Sciences Osaka University

• 松井 宗隆

  Faculty Of Pharmaceutical Sciences Osaka University

• 仁張 総子

  Faculty Of Pharmaceutical Sciences Osaka University

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