30 Phomactin Dの全合成(口頭発表の部)
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Phomactins are novel PAF antagonists isolated from the culture filtrate of the marine fungus, Phoma sp., a parasite on the shell of the crab, Chinoecetes opilio. Their structures, contain a rare bicyclo[9.3.1]pentadecane ring system, were determined based on spectroscopic evidences, X-ray crystallography and chemical conversions. Phomactin D has strongest PAF antagonistic activity among phomactins. Thus its unique structure and biological activity prompted the authors to undertake total synthesis of phomactin D. The sequential Michael reaction of kinetic enolate of 2-cyclohexen- 1-one withα,β-unsaturated ester 2 afforded bicyclo[2.2.2]octane derivative 3 as the sole product. Ketone 3 was converted to olefin 4 in three steps: 1) NaBH_4 reduction, 2) tosylation and 3) elimination of the tosylate. Oxidative cleavage of the C(2)-C(19) double bond in 4 was successfully carried out by ozonolysis followed by NaBH_4 reduction to afford lactone 5. Compound 5 was converted to pentasubstituted cyclohexane derivative 15, having requisite four chiral centers in phomactin D, by chemical modifications. Reaction of alkenyllithium reagent, prepared from alkenyliodide 18 and ^tBuLi, with aldehyde 15 gave alcohol 19 as the sole product. Alcohol 19 was converted to allylic chloride 20. The macrocyclization of sulfone 20 was successfully carried out by treatment with KHMDS to afford 21. Removal of the phenylsulfonyl group and deprotection of benzyl and BOM ether were carried out by treatment of sodium in liq. NH_3 to afford the diol. Epoxidation of the allylic alcohol with ^tBuOOH in the presence of VO(acac)2 gave epoxide as the sole product. Finally, PDC oxidation of the primary and secondary hydroxyl groups completed the synthesis phomactin D (1).
- 天然有機化合物討論会の論文
- 1996-09-02
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