57(P1-5) (+)-ゼストキノンの全合成とその絶対構造の決定(ポスター発表の部)

概要

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We have previously reported the determination of the absolute stereochemistry of the halenaquinol family, marine natural products1-4 isolated from tropical sea sponges, by the theoretical calculation of CD spectra, and also reported the total synthesis of (+)-halenaquinol (1) and (+)-halenaquinone (5).6 In this paper, we report the total synthesis of (+)-xestoquinone (4) and xestoquinol (3), and also describe the determination of their absolute configurations. Optically pure Wieland-Miescher ketone (8aR)-(-)-(15) was converted to enone (+)-(28) via the reactions of eleven steps. The Diels-Alder reaction of (+)-(28) with 3,6-dimethoxybenzocyclobutene (29) yielded adduct (30) of a tetracyclic skeleton, which was converted to (+)-xestoquinone (4) by the reactions of five steps, and then finally to xestoquinol (3). All of the spectroscopic data of the synthetic sample of xestoquinone (4), including the CD data, were identical with those of the natural xestoquinone. Therefore, the absolute configuration of xestoquinone compounds were determined to be 12bS. The CD spectrum of naphthalene-diene derivative (35) were in a good agreement with the theoretically calculated CD curve of the model compound (36). Therefore, the absolute configuration of xestoquinone compounds was also confirmed in a theoretical way. The efficient preparation procedure of optically pure Wieland-Miescher ketone is described.
天然有機化合物討論会の論文
1989-09-17