本論文之全文共分為二部份。第一部份以三氯化鋁為試劑，
研究α-碘基酮73及酯肪酮與各式芳香醛進行aldol縮和反應/消去
反應以合成出新一代抗血管新生化合物。經由酯肪酮或芳香酮上
取代基之不同，亦可用以合成其它烯酮、β-烴基酮與β-氯基酮等
化合物。最後利用此反應條件，以乙醯丙酮作為起始物，成功合成
出Curcumin 62。
本論文第二部份是有關於Guanacastepene A (1)的合成研究。
首先經由四反應步驟合成出雙烯酮化合物114b。利用三氯化鋁催化
Diels-Alder反應之進行，成功建構出七、六駢環骨架化合物116。
將化合物116與各式支鏈進行1,4-加成反應，並以氯化三甲基矽烷
捕捉烯醇陰離子而形成三甲基矽烯醇醚131、134。隨後立刻進行α-
碘基化反應，可得到化合物133和136。另外，利用雙烯酮114b與
4-iodo-1-trimethylsilyl-1-butyne進行1,4-加成反應，並以氯化三甲基
矽烷捕捉形成之烯醇中間體，然後繼續進行α-碘基化反應，可獲得
α-碘基酮143。利用α-碘基酮之自由基環化反應，可成功建構出
七、五駢環骨架分子144a及144b。此外，亦可經二反應步驟合成
出β-位置具甲基取代之雙烯酮化合物114a，並與5-bromo-1-pentene
進行1,4-加成反應，可得到烯酮化合物186。隨後將此烯酮186進行
溴化反應與消去反應後，生成化合物190。最後再加入DBU進行
分子內環化反應，可成功建立C-7與C-9a上具甲基取代的七、六
駢環骨架分子191。

Abstract

The dissertation consists of two chapters. The first chapter describes
the aluminum chloride catalyzed aldol condensation of α-iodo ketone
73 with various aliphatic ketones and aromatic aldehydes and then
to synthesize the small-molecule antiangiogenic analogues of curcumin.
According to the difference of substituent on aliphatic or aromatic
ketones, this method could be applied to the synthesis of diversiform
enones, β-hydroxy orβ-chloro ketones. Finally, the synthesis of
Curcumin 62 was completed by using acetylacetone as starting material
reacted with aluminum chloride and vanillin in an one-step procedure.
The second chapter of this dissertation describes the study of the synthesis of Guanacastepene A (1). The starting material dienone 114b
was synthesized from cycloheptanone in four steps. Diels-Alder reaction
of 114b with trans-1,3-pentadiene using aluminum chloride as a catalyst
gave compound 116 with the 7,6-fused ring skeleton. Treatment of 116
with diverse Grignard reagents in the presence of CuI and TMSCl were
then converted to ketones 133 and 136 by produce silylenolethers 131
and 134. Compounds 131 and 134 α-iodination with NaI and m- CPBA
, respectively. Furthermore, reaction of dienone 114b with Grignard
reagent prepared from 4-iodo-1-trimethylsilyl-1-butyne and Mg to
generate silylenolether 142, followed byα-iodination gave the α-iodo
ketone 143. Application of radical cyclization of α-iodo ketone 143
using ditin gave compounds 114a and 114b with the 7,5- fused ring
skeleton. On the other hand, the dienone 114a with β- methyl group
was synthesized in two steps starting from phorone. Reaction of dienone
114a with Grignard reagent prepared from 5-bromo-1-pentene and Mg
gave compound 186. Treatment of 186 with Oxone®, sodium bromide and
triethylamine produce 190. Finally, reaction of 190 with DBU
underwent intramolecular cyclization to construct the 7,6-fused ring
skeleton 191 with two methyl group at C-7 and C-9a successfully.

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