72 8員環アセタール-アゾメチン構造を有するアントラサイクリン類の合成(ポスター発表の部)

概要

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Barminomycin I and II are a new type of anthracycline antibiotics having a unique substituent at 4'-position and show the equilibrium involving the eight-membered azomethine and carbinolamine. The cytotoxicity of barminomycins against P388 leukemia cells is more than 500 times stronger than that of doxorubicin (adriamycin). The strong activity and unique structure prompted us to synthesize the analog of barminomycin II, 1. The interesting side chain of barminomycin was presumed to be produced from 4'-O-glycoside (24) by the cleavage of vicinal diol with the biological oxidation. Based on this hypothetical biogenesis, the synthetic strategy for 1 was designed. Glycal (14) was prepared from 2-deoxy-D-glucose. Stereoselective halo-glycosidation of N-trifluoroacetyldaunomycin (15) with 14 gave bromo-glycoside (19), which was debrominated with Bu_3SnH and AIBN to afford 20. The critical removal of trifluoroacetyl and benzoyl groups under alkaline condition provided the biogenetic intermediate (24). Periodate oxidation of 24, followed by acidification with acetic acid gave the eight-membered azomethine, (1"R, 5"R)-3"-dehydro-4-O-methylbarminomycin II (1).
天然有機化合物討論会の論文
1990-09-25