139(P-94) 全アルドヘキソースの集約的全合成と手法的活用(ポスター発表の部)
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概要
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A unified diastereo-controlled route to all eight diastereomeric pairs of andohexoses has been explored. Starting from furfural 1, an enantiopure bicyclic enone 5 having a bicyclo[3.2.1]octane framework was first prepared by employing either a lipase-mediated kinetic resolution procedure or a Sharpless asymmetric dihydroxylation procedure. Thus, in the enzymatic procedure, furfural 1 was first transformed into the racemic enone (±)-5, by employing the Achmatowicz rearrangement via the racemic diol (±)-3, which was further transformed into the rac,,emic alcohol (±)-6 and the racemic acetate (±)-7 for lipase-mediated kinetic esterification and kinetic hydrolysis. Both of the substrates afforded enantiocomplemetarily the enantiopure alcohol 6 and acetate 7, respectively, in excellent yields, both of which were reverted into the enone 5 having the corresponding chirality. On the other hand, Sharpless AD reaction of 2 afforded the enantiopure diol 3 in both enantiomeric forms, from which enantiopure enone 5 was obtained in both enantiomeric forms. Owing to the biased framework, the enone 5 exhibited inherent convex-face selectivity which allowed diastereocontrolled modification of the enone functionality to generate the five out of the eight possible trioxygenated diastereomers, DDU-13, DUU-13, UUU-13, UDD-13, and UUD-13, in a diastereoselective manner. Using these five diastereomers, obtained from (-)-5, as the key intermediates, all eight possible L-aldohexoses in addition to four D-aldohexoses have been obtained. Thus, a unified route to all possible diastereomers of aldohexoses has been established.
- 天然有機化合物討論会の論文
- 2000-10-01
著者
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小笠原 國郎
東北大薬
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竹内 美和子
東北大院・薬
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本泉 政敏
東北大院・薬
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谷口 孝彦
東北大院・薬
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小笠原 國郎
東北大院・薬
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Ogasawara Kunio
Pharmaceutical Institute Tohoku University
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