20 Lycoclavaninの構造 : 16-Oxoserratene系トリテルペノイドの相互関連とその部分合成
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概要
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The structure of lycoclavanin, a 16-oxoserratene group triterpenoid occurring in Lycopodium clavatum, was established as (6) by correlation with 16-oxolycoclavanol (5) transforming the each compound into the same keto-diacetate (12). The stereochemistry of cis-α-glycol grouping in ring E was elucidated by application of dibenzoate chirality rule and by inspection of the chemical shift of C_<17>-H signal. Jones' oxidations of 16-oxolycoclavanol acetonide and 16-oxoserratriol acetonide furnished the same keto-aldehyde (16), which on reduction with sodium borohydride in cold exclusively regenerated 16-oxoserratriol (4), thus providing a simple correlation of these triterpenoids. Stepwise transformation of lycoclavanin (6), and 16-oxolycoclavanol (5) into 16-oxoserratriol (4) was also described. Direct correlation of lycoclavanin (6) and serratenediol (28) was successfully achieved by obtaining the same seco-diol (32) as shown in Chart 4. The transformation from lycoclavanin involves the conversion of cis-1,2-glycol into a ketone via tosylation and a stereoselective cleavage of 1,3-glycol monotosylate as key steps. Finally 16-oxoserratenes were synthesized from the corresponding serratenes by oxidation of the latters with limited amount of t-butyl chromate in benzene at 50-60°. Thus serratenediol diacetate, 21-episerratenediol diacetate, serratriol triacetate, and lycoclavanol triacetate afforded naturally occurring 16-oxoserratenediol (1) diacetate, 16-oxoepiserratenediol (2) diacetate, 16-oxoserratriol (4) triacetate and 16-oxolycoclavanol (5) triacetate, respectively.
- 天然有機化合物討論会の論文
- 1969-09-01
著者
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礒部 公明
昭和薬大
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礒部 公明
Showa College of Pharmaceutical Sciences
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遠藤 雅子
昭和薬大
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藤本 琢憲
Showa College of Pharmaceutical Sciences
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津田 喜典
昭和薬大
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藤本 琢憲
昭和薬大
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