P-54 Arnottin IおよびArnottin II : 構造、合成、そのBenzo[c]phenanthridine Alkaloidとの生合成的関連性(ポスター発表の部)
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概要
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Arnottin I (1), C_<20>H_<14>O_6, mp 293-297℃, and arnottin II (2), C_<20>H_<14>O_7, mp 225-226℃, are nonalkaloidal minor components isolated from the bark of Xanthoxylum arnottianum (Rutaceae) by us. Though their structures had remained unknown for a long time because of the isolation of them in low yields, the reexamination of the spectral data of arnottin I (1) (Table 1 for the ^1H NMR) and arnottin II (2) (Table 2 for the NMR) allowed us to deduce their structures to be the same 6H-benzo[d]naphtho[1,2-b]pyran-6-one skeleton as those of gilvocarcin antibiotics and a spiro compound composed of a 3,4-dehydro-1-tetralone and a phthalide skeletons, respectively. Their structures were finally confirmed by the syntheses using the tetralone (3), a synthetic key intermediate of chelerythrine (4) belong to a 2,3,7,8-tetraoxygenated benzo[c]phenanthridine alkaloid, as shown in Scheme 1, because the substituted pattern on their aromatic rings was similar to that of 4. Among them arnottin II (2) was obtained as an optically active form, [α]_<589> -280° (MeOH). Typical negative first (261nm, △ε=-78.5) and positive second (221nm, △ε=+39) Cotton effects were observed in the CD spectrum. (Fig 1) The absolute stereochemistry of the chiral spiro carbon center of arnottin II (2) could be deduced to an R configuration by application of exciton chirality method of the Cotton effects in the CD spectrum. (Fig. 2) Benzo[c]phenanthridine alkaloids are biosynthesized from (S)-reticuline (11) through 6-hydroxyprotopine (12) and 11-hydroxytetrahydrobenzo[c]phenanthridine (13) bases (path A in Scheme 2). The formation of arnottin I (1) and arnottin II (2) in a plant body could be reasonably explained by modification of the biosynthetic route for benzo[c]phenanthridine alkaloids as shown in Scheme 2 [path B for arnottin I (1) and path C for arnottin II (2)], in which the key step is the production of 3-hydroxytetralone (15) by the enzymatic hydrolysis of 11-hydroxytetrahydrobenzo[c]henanthridine base (13).
- 天然有機化合物討論会の論文
- 1995-09-01
著者
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石井 永
千葉大薬
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石川 勉
千葉大薬
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原山 尚
千葉大薬
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石川 勉
千葉大院薬
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渡辺 敏子
千葉大院薬
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室田 雅之
千葉大薬
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渡辺 敏子
千葉大薬
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青木 吉行
千葉大薬
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原山 尚
Faculty Of Pharmaceutical Sciences Kyoto University
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石井 永
Faculty Of Pharmaceutical Sciences Chiba University
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Ishii H
Faculty Of Pharmaceutical Sciences Tokushima Bunri University
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