4 インドール側鎖の選択的酸化による酸化型ジケトピペラジン系アルカロイドの合成

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概要

• 論文の詳細を見る

• DDQ is the only reagent for the selective oxidation of side chains at C-3 of indoles, while oxidation of 3-substituted and 2,3-disubstituted indoles with the other oxidants usually occurs on the pyrrole ring and at the 2-substituent, not at the 3-substituent. This selective oxidation has now been applied to a synthetic work of oxidized diketopiperazine alkaloids, neoechinulin A (NEA) and fumitremorgine B (FTB). Model compounds, diketopiperazines (7 and 8) of tryptophan with glycine and L-alanine, was heated with DDQ in THF to give the corresponding dehydro compounds, 9 (21%) and 10 (60%). The DDQ oxidation of dihydro NEA (12c and 12t) synthesized from indole via several steps was next examined. In t-BuOH, 12 was cleaved to an indole-3-aldehyde (14) through three consecutive reactions, dehydration, addition of t-BuOH, and a retro-aldol reaction. When trichloroethanol was used as a solvent to avoid this side reaction, NEA (1) was isolated in 25% yield. Among other protic and aprotic solvents, dioxane was an only useful solvent. In order to synthesize FTB (15), model experiments via two different pathways involving DDQ oxidation were successfully examined.

• 天然有機化合物討論会の論文
• 1978-08-22

著者

• 及川 裕二

  Faculty Of Pharmaceutical Sciences Hokkaido University

• 及川 裕二

  北大薬

• 米光 宰

  北大薬

• 米光 宰

  北海道大学薬学部

• 米光 宰

  北大 薬

• 吉岡 忠夫

  北大薬

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