29 沖縄産海洋動物Clavularia viridis Quoy and Gaimardに含まれる新規プロスタノイドclavulone I,II,III,IVおよび類縁体の単離と構造

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In connection with our continuing studies on the biologically active constituents of Japanese marine organisms, we have isolated new type of prostanoids, clavulone I(1), II(2), III(3), IV(4) and their congeners 5-8, from the Stolonifer Clavularia viridis Quoy and Gaimard. The structures of these compounds have been elucidated on the basis of spectroscopic data and chemical reactions. Reduction of clavulone I(1) with NaBH_4 gave an alcohol 9, which was oxidized with PCC to give an α,β,γ,δ-unsaturated ketone 11 (Chart 1). Ozonization of 1 gave two aldehydes 12 and 13 (Chart 1). These chemical reactions and analyses of spectral data established the plane structure of clavulone I. Catalytic hydrogenation of 1-3 (Chart 2) and acid-catalyzed isomerization of 1 gave the evidence that 1-4 are the geometrical isomers at carbon-carbon double bonds each other having the same carbon skeleton and oxygen functionalities including the absolute configuration. The geometry of the carbon-carbon double bonds at C-5, -7 and -14 were determined by the ^1H-NMR chemical shifts and coupling constants of the olefin protons as shown in Fig.1. The absolute configuration at C-4 for 1-4 was determined as R by transforming the aldehyde 13 into the lactone 16. The 12-R configuration was elucidated by disclosing the relative stereochemistry (cis) between the C-12 acetoxyl group and C-9 hydroxyl group in 20 on the basis of the presence of intramolecular hydrogen bond between these groups, and then by determining the absolute stereochemistry at C-9 in 9 using exciton chirality method in CD spectrum of 18 (Fig. 2). The structures of 5-8 were determined by comparison of their spectral data with those of 1-4.
天然有機化合物討論会の論文
1983-09-15

29 沖縄産海洋動物Clavularia viridis Quoy and Gaimardに含まれる新規プロスタノイドclavulone I,II,III,IVおよび類縁体の単離と構造

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