金(I)和三氯化鐵共輔佐4-炔醯胺環己-2-烯醇衍生物的分子內環化反應-苯氮呯及六氫吲哚酮衍生物的合成

Abstract

本文分別探討以金、銀與三氯化鐵共輔佐及單獨以三氯化鐵作為路易士酸輔佐4-炔醯胺環己-2-烯醇衍生物進行分子內環化反應。第一部分探討以三氯化鐵輔佐4-炔醯胺-1-矽氧基環己-2-烯醇衍生物，在室溫及氮氣下進行Friedel-Craft反應合成氯化二苯氮呯衍生物。以金、4-炔醯胺-1-矽氧基環己-2-烯醇衍生物銀與三氯化鐵共輔佐4-炔醯胺-1-矽氧基環己-2-烯醇衍生物在室溫及氮氣下生成keteniminium和金碳烯中間體後，進行碳-鹵化反應得到六氫吲哚酮衍生物。第二部分探討4-炔醯胺-1-乙醯氧基環己-2-烯在三氯化鐵輔佐及金、銀與三氯化鐵共催化下，生成keteniminium和碳烯中間體後，進行反式碳－鹵化反應得到六氫吲哚酮衍生物。

This thesis focuses on gold(I)/silver/iron trichloride-copromoted and iron trichloride-promoted intramolecular cyclolization of cyclic 2-enynamides. First, iron trichloride promoted intramolecular cyclization of 1-siloxy-4-ynamidocyclohex-2-enes under nitrogen at room temperature proceeded via Friedel-Craft reaction to produced benzazeprine derivatives. Gold(I)/iron trichloride-copromoted 1-siloxy-4-ynamidocyclohex-2-enes under nitrogen at room temperature afforded oxindole derivatives with good stereoselectivity. The carbohalogenation was suggested via formation of the transient keteniminium ion and gold-carbene intermediates. Second, gold(I)/iron trichloride-copromoted cyclization of 1-acetoxy-4-ynamidocyclohex-2-enes under nitrogen at room temperature generated hexahydroxindole derivatives via carbohalogenation.