112(P48) 紅藻由来の環状ポリケタイド化合物の合成研究(ポスター発表の部)
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Spiroketals or cyclic acetals are often seen in the structure of cyclic polyoxo natural products. However they are mostly acetals or ketals being formed intramolecularly. Cyclic ketals being formed by an intermolecular condensation have rarely been found in nature. Polyoxo cyclic compound 1 is the one which has been isolated from red alga, laurencia chilensis. The structure was determined by X-ray crystallography in 1987 by Fenical et al. Despite of six asymmetric centers, this molecule exists as a racemic form rather than enantiomeric form in nature. This is quite unusual observation for naturally occurring compounds. We are inter-ested in the chemical synthesis and biosynthesis of 1. In nature 1 is assumed to be formed by intermolecular dehydration and acetalization of 2 and 3. Therefore we started preparation of the compounds 2 and 3. The compound 2 was prepared from 1,3-propanediol in 5 steps from mono THP ether of 1,3-propandiol. While, compound 3 was synthesized stereoselectively in 9 steps from cyclohexadiene. The key coupling reaction was performed by aldol addition of ethoxyvinyl lithium to dihydroxydialdehyde, followed by oxidation of the alcohols with Dess-Martin reagent to give an important tetraketone intermediate 4. The structure was confirmed by X-ray crystallographic analysis. Removal of methoxyphenylmethyl group of 4 eventually furnished the synthesis of 3. In this presentation, we will report the above synthesis of 2 and 3, and some attempts of their coupling reaction to 1. 1) M. Bittner, F. Gonzalez, H. Valdebenito, M. Silva, V. J. Paul, W. Fenical, M. H. M. Chen, and J. Clardy, Tetrahedoron Lett., 35, 4031 (1987).
- 天然有機化合物討論会の論文
- 1996-09-02
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