79(P-77) ムール貝下痢性貝毒アドリアトキシンの合成研究(ポスター発表の部)
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概要
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Adriatoxin (1) was isolated as one of the causative toxins of diarrheic shellfish poisoning (DSP) from the digestive glands of DSP-infested mussels, Mytilus galloprovincialis, collected at Emilia Romagna coasts of Italy in 1997. The structure was elucidated in 1998 by using NMR spectroscopic methods, and the ring system is closely related to yessotoxin isolated from toxic scallops in Japan. We report here the improved synthesis of the DEF-ring 5 and the syntheses of the ABCDEF-ring fragment 2 and the HIJ-ring fragment 3 of adriatoxin. The improved synthesis of 5 started from the coupling reaction of triflate (+)-7 and the oxiranyl anion derived from epoxy sulfone 12, and the product 13 was converted into triflate 15. Second coupling of 15 and 16, 6-endo cyclization of 17, and construction of a tertiary alcohol gave 20. Reaction of 21 and oxiranyl anion of 22 followed by 6-endo cyclization and functional group transformations provided fragment 5. Coupling reaction of the triflate 5 with the lithium acetylide 4, ruthenium oxidation, bis(dimethylacetal) formation, and reduction with Et_3SiH-TMSOTf afforded the ABCDEF ring system 2. The key reaction employed in the synthesis of HIJ-ring fragment 3 was a radical cyclization. The cyclization precursor 33c was prepared from aldehyde 30 by reaction with ethynyl magnesium bromide followed by the introduction of acrylate moiety. Treatment of 33c with tributyltin hydride gave the bicyclic 37 after acid treatment. Stereoselective spiro-epoxidation of 37, hydrogenolysis, and the side chain transformation provided cyclic enol ether 41. Epoxidation, protection, reduction, and sulfate-esterification afforded the HIJ-ring fragment 3 of adriatoxin.
- 天然有機化合物討論会の論文
- 2004-10-01
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