路易士酸輔佐六員環4-烯炔醯胺或炔-炔醯胺化合物的分子內環化反應：含氮雙環[3.2.1]辛烷、螺旋[3.5]壬烷及異喹碄的合成

Abstract

摘要 本文分為三個主題，主要為路易士酸輔佐六員環4-烯炔醯胺分子或是六員環1-炔-炔醯胺分子，進行分子內環化反應，合成含氮雙環[3.2.1]辛烷化合物、螺旋[3.5]壬烷化合物以及異喹啉化合物。 （1） 以三氯化鋁輔佐4-炔醯胺環己烯進行分子內環化反應，成功合成含氮雙環[3.2.1]辛烷化合物。酸性條件下，此含氮橋形化合物可經水合反應生成高產率以及高立體選擇性的3-烷醯基-4-氯環已胺化合物，兩者產物皆為天然物重要的骨架。 （2） 以三溴化鐵輔佐六員環炔-炔醯胺進行分子內環化反應，成功合成溴取代之螺旋[3.5]壬烷化合物。此反應路徑由N-keteniminium ion經重排作用得到C-ketenimine，再行環化反應，形成螺旋[3.5]壬烷化合物，此合環反應優點為起始物合成步驟短、使用便宜的三溴化鐵以及反應時間短。 （3） 以金銀共催化1-[（2-炔醯胺）乙基]環己烯化合物進行分子內環化反應，成功合成異喹啉化合物，此合環反應具有操作簡便與溫和的反應條件，得到異喹啉化合物。

Abstract This dissertation covered Lewis acid-promoted intramolecular cyclization reactions of six-membered ring 4-ene- and 1-yne-ynamides afforded 6-azabicyclo[3.2.1]octane, spiro[3.5]nonane, and isoquinoline derivatives. （1） The aluminum(III) chloride-promoted cyclization/chlorination of six-membered ring 4-(N-ethynylamino)cyclohexene enabled a straight forward approach to the 6-azabicyclo[3.2.1]octane. Acid treatment of the resultant chlorinated arylideneazabicyclooctanes furnished 3-alkanoyl-4-chlorocyclohex anamines in excellent yields and high stereoselectivity. （2） The iron(III) bromide-promoted cyclization of six-membered ring 1-yneynamides provided brominated spiro[3.5]nonane derivatives. The reaction mechanism was suggested to proceed via rearrangement of N-keteniminium ion to C-ketenimine followed by cyclization of C-ketenimine generated spiro[3.5]nonane derivatives. The reaction had several advantages: easily available starting materials, inexpensive iron (III) bromide, and short reaction times. （3） The gold (I)-catalyzed intramolecular cyclization of 1-[2-(N-tosyl-N-phenylethynylethyl)]cyclohexene afforded isoquinoline derivatives in fair good yields. The reactions were procedurally simple, efficient, producing isoquinolines under mild reaction conditions. Keywords： Lewis acid, aluminum(III) chloride, iron(III) bromide, enynamides, 1-yneynamides, azabicyclo[3.2.1]octane, spiro[3.5]nonane, isoquinoline