P-45 カルボニルイリドの1,3-双極付加環化反応を機軸とするポリガロリド類の全合成研究(ポスター発表の部)
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概要
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Polygalolide A and B were isolated by Wei and co-workers in 2003 from the roots and stems of Polygala fallax. The structure and relative stereochemical assignment of these molecules were established on the basis of NMR investigations. In conjunction with our continuing interest in the carbonyl ylide cycloaddition strategy for the synthesis of natural products, we embarked on a program aimed at their total synthesis. Herein, we describe our efforts toward a synthesis of polygalolide A. The synthesis of carbonyl ylide precursor 5 commenced with alkylation of the known alcohol 7, readily obtained from D-arabinose (Scheme 2). Oxidative removal of the dithioacetal, followed by Kraus oxidation, esterification with (Boc)_2O, hydrogenation and desilylation furnished alcohol 12. Installation of C2-C3 olefin was accomplished by one-pot Swern oxidation/Mannich reaction and reduction with NaBH_4. Allyl alcohol 13 was converted to 4-methoxyphenyl ether 14 by the two-step sequence. Deprotection of the acetonide, selective silylation, Dess-Martin oxidation and treatment with TFA provided carboxylic acid 6, which was converted to α-diazo ketone 5 via a mixed acid anhydride (Scheme 3). After considerable experimentation with regard to the key cycloaddition reaction, it was found that dropwise addition of 5 to a solution of catalytic Rh_2(OAc)_4 in refluxing C_6H_5CF_3 afforded the desired cycloadduct 3 as a single isomer in 73% yield (Table 1). The cycloadduct 3 was uneventfully transformed to tetracyclic lactone 20 (Scheme 4). Finally, the reaction of zinc enolate derived from 20 with aldehyde 21, followed by acetylation, β-elimination and deacetylation completed the total synthesis of polygalolide A (Scheme 5).
- 天然有機化合物討論会の論文
- 2005-09-15
著者
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橋本 俊一
北大院薬
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菊地 史朗
北大院薬
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中村 精一
北大院薬
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菅野 幸人
北大院薬
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橋本 俊一
Fac. Of Pharmaceutical Sciences Hokkaido Univ. Sapporo 060-0812 Jpn
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中村 精一
Faculty Of Pharmaceutical Sciences Hokkaido University
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