5 (±)-Lycoramineの全合成
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概要
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The racemic modification of lycoramine (I), an alkaloid isolable from Lycoris radiata has been synthesized by two routes. Starting from 2-hydroxy-3-ethoxybenzaldehyde the cyano-ketone (XI) was prepared by the standard method and reduced with lithium aluminum hydride to give the hydroxy-aldehyde (XII). The Wittig reaction with the acetate of (XII) afforded the acrylate (XVI) which was transformed to the tetralone (XIX) in the usual manner. Schmidt reaction on the tetralone (XIX) gave two isomeric lactams (XX and XXI) in a ratio of 3:2. The desired lactam (XXI) was selected by snectral data, N-methylated, deacetylated and oxidized, yielding the keto-lactam (XXIV). This compound was obtained from natural lycoramine through a sequence of reactions, including catalytic hydrogenolysis of the furan ring in the ethyl analog (XXVb) of oxolycoraminone (XXVa) in an alkaline solution. Since the keto-lactam (XXIV) was convertible into (+)-lycoramine by a sequence of reactions including bromination, dehydrobromination, demethylation, methylation, and lithium aluminium hydride reduction, the synthesis of (±)-lycoramine was completed. The key intermediate in the second method involved the 1,3-diketone (7), which was obtained by the Claisen condensation of the keto-ester (6). Monoketalization of the diketone (7) followed by lithium aluminum hydride reduction and hydrolysis of the ketal grouping gave the perhydrobenzopyran (10). Hydrolysis of the methoxyl group and cleavage of the pyran ring with constant boiling hydriodic acid and concomitant recyclization afforded the phenol (11). Through a sequence of 7 steps, the phenol (11) was transformed to the tetralone (18) which was subjected to the Schmidt reaction, giving two isomeric lactams (19 and 20). The desired lactam (20) was N-methylated and treated with lithium aluminum hydride to furnish the end product, (±)-lycoramine (XXXI).
- 天然有機化合物討論会の論文
- 1967-09-25
著者
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吉武 彬
京都大学薬学部
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入江 寛
Faculty Of Pharmaceutical Sciences Kyoto University
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上尾 庄次郎
京都大学薬学部
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新宮 徹朗
京大薬
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新宮 徹朗
京都大学薬学部
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Shingu K
School Of Pharmacy Kobe Gakuin University
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入江 寛
京都大学薬学部
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水谷 民雄
京都大学薬学部
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高田 将夫
京都大学薬学部
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狭間 直彦
京都大学薬学部
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関戸 守
京都大学薬学部
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三坂 義治
京都大学薬学部
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