53 ヨヒンビンおよび関連アルカロイドの合成研究
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概要
- 論文の詳細を見る
Total synthesis of two alkaloids, (±)-yohimbine (11) and (±)-alloyohimbine (12), has been accomplished by regioselective functionalization of 18-dehydroyohimbones (16) and (17) which were readily prepared via reductive photocyclization of the enamide (13). Synthetic study of reserpine-type of alkaloids by the same methodology is also investigated. Although reductive photocyclization of the 4-methoxy-3-methoxycarbonyl-substituted enamide (4) afforded not the desired lactam (7) but two lactams (5) and (6), three reactions sequence, consisting of reductive photocyclization of the 4-methoxy-substituted enamide (13) followed by reduction of the lactam-carbonyl group and hydrolysis of the enol-ether group, provided a good yield of the unconjugated enone (15) which was useful as a key intermediate in our total synthesis. Stereoselective isomerization of the enone (15) with tartaric acid at 85°gave the D/E-trans-enone (16) which was first lithiated under the kinetically controlled condition and then converted into the corresponding magnesium enolate and finally quenched with methyl chloroformate to afford yohimbinone (21) regioselectively which was further converted into (±)-yohimbine upon reduction. Similarly, alloyohimbinone (23) was synthesized from the D/E-cisenone (17) which was stereoselectively prepared by treatment of the key intermediate (15) with silica-gel. The dimethoxy-substituted enamide (24) was also converted into the key intermediate (26) for the synthesis of reserpine-type of alkaloids.
- 天然有機化合物討論会の論文
- 1983-09-15
著者
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平田 由美子
Kobe Women's College Of Pharmacy
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宮田 興子
神女薬
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平田 由美子
神女薬
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内藤 猛章
神女薬
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二宮 一弥
神女薬
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内藤 猛章
神戸女子薬科大学
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二宮 一彌
神戸女薬大
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二宮 一弥
神戸薬大
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内藤 猛章
神戸薬科大学
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