55 Benzoquinolizidine環系ウリノキ科アルカロイドの一般的合成法
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概要
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The target molecules (±)-25a and (±)-25b were selected for synthesis with a view to establishing new synthetic routes to some ipecac and Alangium lamarckii alkaloids having the 9,10-dimethoxy- and 8-hydroxy-9,10-dimethoxybenzo[a]quinolizidine skeletons. The synthesis of (±)-25a has been accomplished by means of an initial condensation of 3-(1,1-ethylenedioxyethyl)pyridine (12) with 3,4-dimethoxyphenacyl bromide (13a) and succeeding steps proceeding through the intermediates 14a, 15a, 16a, 17a, 18a, 19a, 20a, 21a, 22a (or 24a), and 23a. A parallel synthesis starting with 12 and 2-benzyloxy-3,4-dimethoxyphenacyl bromide (13b) afforded (±)-25b in good overall yield through 14b, 15b, 16b, 17c, 18c, 18b, 19b, 20b, 21b, 22b (or 24b), and 23b. The intermediate 18a was alternatively prepared from 12 through 30a, 31a, 32a, and 17a, or from 3-(1,1-ethylenedithioethyl)-pyridine (33) through 34a and 35a. By a parallel series of conversions, 18c was also synthesized from 12 or 33. In view of the previous conversions of (±)-25a into (-)-emetine (8), (±)-cephaeline, (±)-protoemetinol, (±)-tubulosine, (±)-deoxytubulosine, (+)-O-methylpsychotrine, (±)-protoemetine, and (±)-emetamine and those of (±)-25b into (±)-ankorine (1), (±)-alangicine (2), and (±)-alangimarckine (3), the present syntheses of (±)-25a and (±)-25b constitute formal new syntheses of these alkaloids. Since the starting material 12 or 33 is obtainable from 3-acetylpyridine, the method used for the above syntheses may be called "3-acetylpyridine method" for convenience of ready reference.
- 天然有機化合物討論会の論文
- 1983-09-15
著者
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大場 正志
Kanazawa Univ. Ishikawa Jpn
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大場 正志
金沢大薬
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藤井 澄三
金沢大薬
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秋山 茂明
Faculty of Pharmaceutical Sciences, Kanazawa University
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Ohba M
Faculty Of Pharmaceutical Sciences Kanazawa University
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秋山 茂明
Faculty Of Pharmaceutical Sciences Kanazawa University
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秋山 茂明
金沢大薬
関連論文
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- 55 Benzoquinolizidine環系ウリノキ科アルカロイドの一般的合成法
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