摘要
環戊烷結構為許多天然物中常見的單位，本論文以簡便的方法合成具有立體選擇性的環戊烷衍生物。本文旨在利用金銀共催化系統對帶有炔基的烯醇化物進行分子內克萊森類型重排反應，得到具非鏡像選擇性帶有乙烯基和酮基的1,2-雙取代環戊烷衍生物。

5-己炔-1-醇與芳香環碘化物在鈀金屬催化下進行Sonogashira反應得到6-芳香環-5-己炔-1-醇，以2-碘酰基苯甲酸 (IBX, 2- iodoxybenzoic acid)氧化劑氧化得到6-芳香環-5-己炔-1-醛後，再和溴化2-乙氧-2-側氧乙基三苯基鏻((2-ethoxy-2-oxoethyl)triphenylphosphonium bromide)進行Wittig 反應得到8-芳香環-2-烯-7-炔辛酸乙酯，以二異丁基氫化鋁還原得到8-芳香環-2-烯-7-炔-1-辛醇。

將此帶有炔基的烯醇化合物與0.10當量的氯化三苯基磷金/三氟甲磺酸銀 (Ph3PAuCl/AgOTf)溶於甲苯溶劑，在迴流中，進行分子內克萊森類型重排反應得到帶乙烯基和酮基的-1,2-雙取代環戊烷。以X-ray繞射分析證明環化產物中的乙烯基和酮基為反式的1,2-雙取代環戊烷。

The cyclopentanes are frequently found in a variety of natural products. Therefore, the development of practical and facile synthetic routes for the synthesis of stereoselective five-membered ring derivatives is important. In the thesis, we report that gold and silver cocatalyzed intramolecular Claisen-type rearrangement of (E)-8-phenyloct-2-en-7-yn-1-ol (enynol) produces 1-phenylcarbonyl-2-vinylcyclopentanes in diastereoselective fashion.

Reaction of hex-5-yn-1-ol with aryl iodine catalyzed by palladium(0)under Sonogashira reaction conditions produces 6-arylhex-5-yn-1-ol. Oxidation of 6-arylhex-5-yn-1-ol with IBX (2- iodoxybenzoic acid) affords 6-arylhex-5-yn-1-al. The resulting aldehyde was treated with (2-ethoxy-2-oxoethyl)triphenylphosphonium bromide to afford (E)-ethyl
8-phenyloct-2-en-7-ynoate. Reduction of the (E)-ethyl-8-phenyloct-2-en-7-ynoate using DIBAL(Diisobutylaluminium hydride) generated (E)-8-phenyloct-2-en-7-yn-1-ol.

Treatment of the enynol with 10 mol % Ph3PAuCl / AgOTf in toluene at reflux produced 1-phenylcarbonyl-2-vinylcyclopentanes. The formation of the cyclopentane derivative is believed to undergo intramolecular Claisen-type rearrangement. The X-ray diffraction analysis reveals that the relative stereochemistry of the vinyl and the keto is trans.

目錄
中文摘要 I
英文摘要 II
縮寫對照表
第一章 緒論 1

第二章 金(I)離子催化烯炔醇化物合成單一非鏡像選擇性1,2-雙取帶
環戊烷衍生物
2.1前言 8
2.2實驗設計與概念 34
2.3 結果與討論
2.3.1 (E)-8-芳香環-2-烯-7-炔-1-辛醇合環前起始物製備
A. 6-芳香環-5-己炔-1-醇化物製備 37
B. 6-芳香環-5-己炔-1-醛化物製備 38
C. (E)-8-芳香環-2-烯-7-炔辛酸乙酯化物製備 40
D. (E)-8-芳香環-2-烯-7-炔-1-辛醇化物製備 41




2.3.2 金(I)離子催化烯炔醇化物合成單一非鏡像選擇性1,2-雙
取帶環戊烷衍生物 43
2.3.3 未來展望─天然物全合成 Brefedin C 62
2.4 結論 64


第三章 實驗部份
3.1 分析儀器及基本實驗操作 65
3.2 金(I)離子催化烯炔醇化物合成單一非鏡像選擇性1,2-雙取代環
戊烷衍生物 67
3.2.1 一般實驗程序 67
3.2.2. (E)-8-芳香環-2-烯-7-炔-1-辛醇合環前起始物製備 70
3.2.3 金(I)離子催化烯炔醇化物合成單一非鏡像選擇性1,2-雙取
帶環戊烷衍生物 104

參考文獻 115

附錄

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