22 Dihydrolycorineの合成
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概要
- 論文の詳細を見る
The synthesis of dihydrolycorine, the sole hydrogenation product of lycorine, which is the main alkaloid of Lycoris radiata and a number of other species of the Amaryllidaceae, has been accomplished in the following way. Methanolysis of the anhydride (X) followed by the Friedel-Crafts cyclization with phosphorus pentachloride and stannic chloride gave the hydrofluorenone-ester (VIII) and the tetralone-ester (XIII). Reduction of the former (VIII) with lithium aluminum hydride gave the diol (XIV) which was re-oxidized with activated manganese dioxide to the keto-alcohol (XV). Schmidt reaction of (XV) with sodium azide in trichloroacetic acid and subsequent alkaline hydrolysis gave the hydroxy-lactam (XVI) along with a by-product of unknown structure. The hydroxy-lactam (XVI) was converted into the cyanolactam (XVIII) by tosylation followed by treatment with potassium cyanide. Acidic hydrolysis of (XVIII) gave the lactam-acid (IV), whose stereo-structure was comfirmed by its transformation into γ-lycorane (XIX). Treatment of (IV) with iodine and potassium iodide in aqueous sodium bicarbonate gave the iodo-lactone (XXII) which was easily converted into iodo-acetyl-imide (XXV) in acetic acid and acetic anhydride. Elimination of hydrogen iodide from (XXV) with lithium chloride in DMF yielded the olefine (XXVI) which was oxidized by m-chloroperbenzoic acid in chloroform to the epoxide (XXVII). Reduction of (XXVII) with a mixture of lithium aluminum hydride and zinc chloride in THF furnished (±)-dihydrolycorine which was identical with natural dihydrolycorine in the n.m.r. and mass spectra. Furthermore, the i.r. spectrum of the O-diacetyl derivative of this synthetic compound was superimposable on the spectrum of diacetyldihydrolycorine from natural sources.
- 天然有機化合物討論会の論文
- 1970-10-01
著者
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入江 寛
Faculty Of Pharmaceutical Sciences Kyoto University
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杉田 稔
京都大学薬学部
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入江 寛
京大薬
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上尾 庄次郎
京大薬学部
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西谷 康宏
京都大学薬学部
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西谷 康宏
京大薬
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杉田 稔
京大薬
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