72 光フリース転位反応を利用したインドールアルカロイドの合成研究

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概要

• 論文の詳細を見る

• With an interest in application of photoreactions to the alkaloid synthesis, a solution of the acyl tryptamine derivative 3 in throughly N_2-saturated methanol was submitted to irradiation with a mercury lamp to afford the nine membered lactam 5 in a good yield, which was prove to be an important intermediate for the total syntheses of tubifoline 18 and condyfoline 19 by modification of the Harley-Mason's method. On these studies, it was found that iodine pentoxide (I_2O_5) is a good selective oxidant for the oxidation of the alkanyl side chain at C-2 position of indoles, and cyclization of 14 provided the tetracyclic ketoamide 15 as a diastereomeric mixture. The trans isomer was epimerized to the cis isomer 15 in chloroform at room temperature, which was established by direct comparison with the authentic sample. This photoreaction was now extended to the synthetic approach to iboga alkaloids. As a preliminary work to know whether or not the above photoreaction could be available in the secondary amines, the N-benzyl derivative was irradiated to afford 24. Also, 23 reacted with HCHO in acetic acid to give the spiro compounds, 25 and 26, indicating that the nuclephilicity of 3-position in N-acyl indoles is still alive. When the primary amine 3 was heated with aq. HCHO in formic acid for 30 min., the pentacyclic amine 28 was obtained in 70% yield without generation of N,N-dimethyl derivative. The spiro-compound 28 was heated with oxalic acid in ethanol at reflux up afford the desired amine 30, which was irradiated with a mercury lamp to give the bicyclic lactam 31. The compound 31 constiutes a principal part of the unique skeleton of iboga alkaloids.

• 天然有機化合物討論会の論文
• 1979-09-20

著者

• 伴 義雄

  北大・薬

• 伴 義雄

  東邦大・薬

• 伴 義雄

  Faculty Of Pharmaceutical Sciences Hokkaido University

• 大石 武

  北大・薬:(現)理化学研究所

• 小林 克彦

  北大・薬

• 吉田 清史

  北大・薬

• 後藤 二郎

  北大・薬

• 石ヶ森 えい子

  北大・薬

• 後藤 二郎

  Faculty. Of Pharmaceutical Sciences Hokkaido University

• 吉田 清史

  北大・薬:(現)明治制菓(株)中央研究所

• 石ヶ森 えい子

  北大・薬:(現)北里大学医学部

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