(+)-Aspicilin的合成

Total synthesis of (+)-Aspicilin

王淳逸(Chun-yi Wang)

指導教授 ： 侯敦仁

國立中央大學/理學院/化學系/碩士(2010年)

摘要

利用掌性的雙烯雙醇((3R,4R)-hexa-1,5-diene-3,4-diol)87為起始物合成(+)-Aspicilin。在此我們利用雙烯雙醇87保護後進行Sharpless 環氧化反應，建構出第三個掌性中心。再與丙二酸二乙酯(diethyl malonate)反應得到內酯化合物。接著進行水解反應，形成羧酸化合物，再與具有掌性中心的(S)-十一烯二正十二醇((S)-dodec-11-en-2-ol)進行酯化反應。利用環閉合置換反應，合環得到十八圓環的內酯。以二異丙胺鋰拔掉內酯的α位置氫與苯硒官能基硒化，接著用過氧化氫氧化生成共軛雙鍵，得到天然物(+)-Aspicilin。

關鍵字

酯化反應 ； 環閉合置換 ； 天然物 ； 有機合成

並列摘要

(+)-Aspicilin was synthesized using (3R,4R)-hexa-1,5-diene-3,4-diol as the starting material. We applied Sharpless epoxidation to create the third chirality center. Diethyl malonate was used to attack the epoxide to produce lactone, which was hydrolyzed to give acid. Esterification of acid and (S)-dodec-11-en-2-ol was achieved by Yamaguchi esterification. Ring cross metathesis (RCM) was applied to give the 18-membered ring macrolactone. The synthesis of (+)-aspicilin was completed by hydrogenation, selenylation, oxidation, and deprotection.

並列關鍵字

total synthesis ； RCM ； Ring crossing metathesis ； aspicilin ； esterification

參考文獻

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