本論文是敘述 eunicellin (cladiellin) 骨架之雙帖類化合物：Simplexins A的合成研究。以蒎烯110為起始物經兩步反應可輕易的製備出烯酮109。與支鏈130進行1,4加成反應，接著利用碘化反應得到α-碘基環酮108。以分子內自由基環化反應為關鍵步驟建立起順式 (cis) 駢環，再利用 [1,5] 氫轉移使雙鍵位移得到新的駢環化合物123。利用臭氧裂解切開五環可以得到帶有醛基與酮基兩種官能基的化合物125，雖然有部分化合物125會溶劑中的甲醇進行反應產生半縮醛化合物124，但是很幸運的發現可以利用三氟醋酸將此半縮醛解開反應回化合物125。利用乙二醇選擇性保護反應性較高之醛基成為化合物126，最後與丙烯醛134進行aldol反應成功的合成出化合物127。在未來可以化合物127為中間體應用於天然物Simplexins A 之全合成。

In this thesis, we investigated the synthesis of nature product Simplexins A which was an eunicellin (cladiellin) diterpene. We prepared enone 109 from piene 110 via two tandem reactions. Treatment of compound 109 with side chain 130 underwent 1,4-addition and iodination to yield α-iodo ketone 108. We used atom-transfer cycloaddition as the key step to constract the cis-hydrindanone. The compound 123 was obtained through double bond migration and [1,5] hydride shift. The five-member ring of compound 123 was cleavaged by ozonolysis to give compound 125 containing a ketone and an aldehyde group. Despite compound 125 would react with methanol solvent and gave hemiacetal compound 124. Fortunately, we could get compound 125 again by using trifluoroacetic acid. Using ethylene glycol to protected the highly reactive aldehyde gave compound 126. Furthermore, the aldol reaction of compound 134 with acrolein was carried out and generated compound 127. Compound 127 could be an intermediate and have applications to the total synthesis of Simplexins A.

目錄………………………………………………………………i
縮寫對照表………………………………………………………ii
第一部分：天然物Simplexins A之合成研……………………1
第一章：緒論……………………………………………………2
§ 1-1 Simplexins A的單離、藥性及結構………………2
§ 1-2 Eunicellin骨架之天然物的合成文獻回顧………6
§ 1-3 Simplexins A之研究構想與逆合成分析…………19
第二章：實驗結果與討論………………………………………22
第三章：結論……………………………………………………34
第四章：實驗部分………………………………………………37
§ 4-1一般實驗敘述 ………………………………………37
§ 4-2實驗步驟與光譜資料 ………………………………40
參考文獻…………………………………………………………56
附錄目……………………………………………………………59

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