中文摘要

本論文旨在研究掩飾鄰苯醌之反應及其合成應用，內容共分為兩部份：第一部係探討雙環[2.2.2]辛烯酮硫化物及硒化物Raney-Nickel或Bu3SnH/AIBN之反應研究；第二部份則討論掩飾鄰苯醌6f與呋喃107應用於天然物(±)- eudesmadieneolide (91)之合成研究。
第一部份: 以掩飾鄰苯醌6與苯基乙烯基硫醚及苯基乙烯基硒醚分別進行分子間Diels-Alder反應，可得高產率之雙環[2.2.2]辛烯酮硫化物20與硒化物21，接著分別與Raney-Nickel或與Bu3SnH/AIBN進行去硫及去硒反應，主要是獲得直接還原產物61、部份的ODPM-重排產物65及過度還原產物67，特別的是無DPM-重排產物生成，此結果異於文獻報導，推測原因是由掩飾鄰苯醌6之取代基所造成的影響。另一方面，我們發現當硫化物20a及20c分別與Bu3SnH/AIBN進行反應時，可得一特殊重排產物74a及74c，重點是其機構並不是經DPM或ODPM之反應路徑，推測是由正三丁錫自由基與碳氧雙鍵加成後再進行重排所得到的。

第二部份: 以市售香草醛109為起使物，其醛基經保護後，以二乙醯氧基碘(III)苯氧化可得掩飾鄰苯醌6f，接著與呋喃107進行分子間Diels-Alder反應可得化合物108f。化合物108f與溴甲苯進行反應可得化合物115，接著再與溴化乙烯基鎂進行1,2-加成反應，得到二個異構物116a及116b，比例為12 : 1，以異構物116a及116b進行陰離子oxy-Cope重排反應，可成功獲得順式十氫萘骨架化合物117，經水解、氫化及氧化斷裂反應可得內酯120，目前已完成內酯120的合成，希望經由數步官能基轉換能合成出天然物eudesmadieneolide (91)。

Abstract

This thesis, which is divided into two parts, aims on the studies of masked ortho-benzoquinones (MOBs) and their applications. The first part is concerned with the novel radical reactions of bicyclo[2.2.2]octenones 20 and 21 utilizing Raney-Nickel or Bu3SnH/AIBN as reducing agents. In the second part, the investigation towards the total synthesis of (±)-eudesmadieneolide (91) is described.
PartⅠ: Diels-Alder reactions of masked o-benzoquinones (MOBs) 6 with phenyl vinyl sulfide and phenyl vinyl selenide furnished bicyclo[2.2.2]octenones 20 and 21 with exceptional regio- and stereoselectivity. Treatment of compounds 20 and 21 with Raney-Nickel or Bu3SnH/AIBN afforded the major product compound 61 and the minor ODPM-rearrangement product 65, respectively without the isolation of any DPM rearrangement product. This phenomenon is different from literature reports. We believe that the substituents with various electronic properties present on MOBs 6 have a strong effect on these reactions. Furthermore, the functionalities, namely sulfur and selenide, which were introduced from the dienophiles used in the Diels-Alder reactions of MOBs and phenyl vinyl sulfide and phenyl vinyl selenide, also played an important role to direct the reaction pathway. Furthermore, we also found the desulfurization of compound 20a and 20c with Bu3Sn H/AIBN could provide novel compounds 74a and 74c, respectively. Surprisingly, formation of these two products is independent on the reaction pathway of DPM and ODPM rearrangement. However, a mechanism is proposed by us where tri-n-butyltin radical is presumably first added to the oxygen of carbonyl group followed by undergoing rearrangement to furnish 74a and 74c.

PartⅡ: The tricyclic compound 108f was obtained via intramolecular Diels-Alder reaction of MOB 6f with furan 107. Protection of compound 108f followed by 1,2-addition and anionic oxy-Cope rearrangement successfully afforded cis-decalin 1117. Transformation of compound 117 into compound 120 was carried out in consecutive steps, including hydrogenation, hydrolysis and oxidative cleavage. Thus the core structure of natural product (±)-eudesmadieneolide (91) was obtained which can be easily converted to 91 upon few functional group transformation.

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