115(P-46) Kalihinane型ジテルペノイドの探索と合成(ポスター発表の部)
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Three new kalihinane-type diterpenoid, Δ^9-kalihinol Y (1), 10-epikalihinol I (2) and 5,10-bisisothiocyanatokalihinol G (3) were isolated along with previously isolated kalihinane-type diterpenoids kalihinol A (4), kalihinene (5) and 6-hydroxykalihinene (6) from the Okinawan marine sponge, Acanthella sp. Kalihinol A and related compounds were noted to possess remarkable in vitro antimalarial activity (Table 1). The absolute configuration of kalihinol A (4) was determined by applying the CD exciton chirality method to bis-p-bromobenzamide 8, which was derived from kalihinol A (4) (Scheme 1 and Fig. 1). This is the first determination of the absolute configuration of kalihinane-type diterpenoid. Synthetic studies on kalihinol A (4) and kalihinene X (9) were carried out by using intramolecular Diels-Alder reaction as a key step (Scheme 2-7). Sulfone 11 was prepared from glycidol via coupling reaction of methyl phenyl sulfone (Scheme 2). Epoxyalcohol 14 was prepared from geraniol via asymmetric dihydroxylation and asymmetric epoxidation (Scheme 3). Coupling reaction of sulfone 11 with epoxyalcohol 14 in the presence of "BuLi, followed by removal of phenylsulfonyl group and acetylation gave acetate 15 (Scheme 4). Acetate 15 was converted to triene 17 in several steps. Intramolecular Diels-Alder reaction of enone, prepared by hydrolysis of triene 17, was carried out to give cis-decalin 18 as the sole product (Scheme 5). cis-Decalin 18 was converted to nitrile 19 in 2 steps. Total synthesis of kalihinene X (9) from nitrile 19 is being carried out. cis-Decalin 18 was treated with NaOMe to give a mixture of cis-decalin 18 and trans-decalin 20 (18:20=10:1) (Scheme 6). Intramolecular Diels-Alder reaction of triene 17 was carried out to give a mixture of trans-decalin 21 and cis-decalin 22 (21:22=1:1) (Scheme 7). Improvement of diastereoselectivity in the intramolecular Diels-Alder reaction and total synthesis of kalihinol A (4) from trans-decalin 20 are being investigated.
- 天然有機化合物討論会の論文
- 2000-10-01
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