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壹、天然物(±)-□9(12)-Capnellene之合成研究 ; 貳、天然物(+)-Eudesmadiene-12,6-olide之合成研究
Thesis

壹、天然物(±)-□9(12)-Capnellene之合成研究 ; 貳、天然物(+)-Eudesmadiene-12,6-olide之合成研究

周宥佑
Masters, National Tsing Hua University
2009

Abstract

線形參環環戊烷掩飾鄰苯?Diels-Alder反應陰離子oxy-Cope重排反應全合成ODMP重排順式十氫?(±)-D9(12)-capnellene(+)-eudesmadiene-12,6-olide triquinanesmasked o-benzoquinoneDiels-Alder reactionoxy-Cope rearrangementtotal synthesisoxa-di-pi-methane rearrangementcis-decalin(±)-D9(12)-capnellene(+)-eudesmadiene-12,6-olide
The thesis consists of two parts: the first part describes the total synthesis of triquinanes natural product (±)-□9(12)-capnellene(1). The second part illustrate the total synthesis of sesquiterpene lactones (+)-eudesmadiene-12,6-olide (100).The linear triquinane 89 was obtained by sequential intermolecular Diels-Alder reaction of masked o-benzoquinone generated in situ by DAIB mediated oxidation of 2-methoxy-4-methylphenol (82) in methanol followed by demethoxylation, dialkylation, photochemical oxa-di-□-methane rearrangement and opening of a strained cyclopropane ring. The transformation of triquinane 89 into compound 1 was achieved by functional group transformations.The tricyclic compound (+)-138a was obtained via intramolecular Diels-Alder reaction of MOB 136a with homochiral furan (+)-137a. Protection of compound (+)-138a, followed by coupling reaction, 1,2-addition and anionic oxy-Cope rearrangement successfully afforded cis-decalin 142. Transformation of cis-decalin 142 into compound 149 was carried out in consecutive steps, including reduction, hydrolysis, hydrogenation and oxidative cleavge. Thus the core structure of natural product (+)-eudesmadiene-12,6-olide (100) was obtained which can be easily converted to 100 a few functional group transformations.

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