路易斯酸輔佐七員環2-烯炔醯胺及呋喃炔醯胺化合物的環化反應：稠雙環γ-內醯胺與吡咯衍生物的合成

Abstract

本論文包含兩個主題，主題一：利用三氯化鐵輔佐2-烯炔醯胺七員環化合物，進行分子內環化反應，合成雙環[5.3.0]-γ-內醯胺化合物，主題二：利用三氯化金催化具有炔醯胺側鏈的呋喃化合物，進行分子內環化反應，合成吡咯衍合物。 主題一為三氯化鐵輔佐2-烯炔醯胺七員環化合物，進行分子內環化反應，合成具四個立體中心的含氯雙環[5.3.0]-γ-內醯胺化合物，此反應的優點為操作簡單、條件溫和且不需額外添加氧化劑即可合成含氯雙環[5.3.0]-γ-內醯胺化合物。 主題二探討有效率合成順式-3-芳香基取代-4-(側氧基-1-丙烯基)吡咯衍合物，在氮氣條件下，以三氯化金催化C-2位置具炔醯胺側鏈的呋喃化合物，可快速合成吡咯衍合物，此反應操作簡單、溫和條件且產率良好。The thesis contains two topics. The first part is the synthesis of chlorinated bicyclo[5.3.0]-γ-lactams via iron(III) chloride-catalyzed intramolecular cyclization of seven-membered ring 2-enynamides. The second part is the synthesis of pyrrole derivatives via gold(III)-catalyzed intramolecular cyclization of ynamide-tethered furans. A simple and mild process was developed for the synthesis of chlorinated bicyclo[5.3.0]-γ-lactams, possessing four stereocenters, from easily available seven-membered ring 2-enynamides. The reaction required only an inexpensive iron(III) chloride under dry air and were tolerant of aryl and heteroaryl groups at the alkyne terminus. An efficient synthesis of 3-aryl-substituted-4-(3-oxopropen-1-yl)pyrroles is developed. Treatment of gold(III) chloride with furans containing a tethered ynamide at the C-2 position of the furan ring in toluene under nitrogen proceeds rapidly to afford pyrrole derivatives in good yields. The reactions are operationally simple and under mild reaction conditions.