P-90 抗菌活性化合物ボトシニン酸類の全合成(ポスター発表の部)
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概要
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Botcinolide (1) was isolated from culture broth of Botrytis cinerea as a significant phytotoxic metabolite in 1993 by Cutler et al. The relative configuration of 1 was suggested based on the spectroscopic analysis by the same group. In 1996, Collado et al. isolated other metabolites from B. cinerea (strain UCA 992) related to 1 named 4-O-methylbotcinolide (2), 3-O-acetyl-5-O-methylbotocinolide (3), 2-epibotcinolide (5), and 3-O-acetyl-2-epibotcinolide (6). In the same year, homobotcinolide (4) was also isolated from B. cinerea by Cutler. After one decade, Nakajima et al. obtained metabolites botcinic acid (7), botcinin E (11), and botcinin A (12) from the culture filtrate of a different strain of B. cinerea (strain AEM 211) and some of them showed antifungal activity against Magnaporthe grisea, a pathogen of the rice blast disease. Nakajima first assigned their forms and later reported that the structure of botcinolide (1) should be revised to that of 7, the structure of 4-O-methylbotcinolide (2) should be revised to that of botcinic acid methyl ester (8), and the structure of 3-O-acetyl-2-epibotcinolide (6) should be revised to that of 12. They also expected that the structures of 3-O-acetyl-5-O-methylbotcinolide (3), homobotcinolide (4) and 2-epibotcinolide (5) should be revised to those of 3-O-acetylbotcinic acid methyl ester (9), botcineric acid (10), and 11, respectively, based on the studies of the chemical conversion of the botcinic acid derivatives and comparison of their spectroscopic data. Recently, we have established methods for the syntheses of botcinins C (13), D (14), and F (15), and the proposed structure of 2-epibotcinolide (5) by the stereoselective aldol reactions and a rapid lactonization using MNBA. We concluded that the reported nine-membered ring structures of 2-epibotcinolide (5) and other related compounds are extremely doubtful based on the detailed comparison of the ^1H NMR spectrum of the synthetic intermediates with natural products. In this presentation, we will show the first total synthesis of the botcinic acid analogues (7-10) and botcinin E (11) which have updated the proposed structures of botcinolides (1-5) in order to show the true forms of these natural products.
- 天然有機化合物討論会の論文
- 2008-09-01
著者
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福井 博喜
東京理科大学理学部
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椎名 勇
東京理科大学理学部
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福井 博喜
東理大理
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椎名 勇
東理大理
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椎名 勇
Department Of Applied Chemistry Faculty Of Science Tokyo University Of Science
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