路易斯酸輔佐六員環炔‒炔醯胺與呋喃炔醯胺及環己烯炔‒炔醯胺化合物的環化反應：螺旋[3.5]壬烷、吡咯與γ-內醯胺衍生物的合成

Abstract

本文分為三個主題，分別探討利用不同的路易斯酸催化六環炔‒炔醯胺化合物、呋喃炔醯胺化合物與六員環烯炔-炔醯胺化合物進行分子內合環反應，分別合成出螺旋[3.5]壬烷化合物、吡咯化合物與γ-內醯胺化合物。

（一） 以三溴化鐵催化六員環炔-炔醯胺進行分子內環化反應，成功合成具溴加成之螺旋[3.5]壬烷化合物。此反應路徑先進行N- to C-的轉移，再經由aza-Prins-cyclization，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，另外在甲氧基與噻吩取代時，會形成具有cumulene的中間體，再經由[2 + 2]環化加成反應，得到長共軛的亞胺化合物。

（二） 利用三氯化金催化呋喃炔醯胺化合物進行分子內環化反應，得到順式 -3-芳香基取代-4-(側氧基-1-丙烯基)吡咯衍生物。此反應推測會形成gold carbene的中間體後得到吡咯衍生物。此反應的優點為條件溫和、反應時間短以及產率良好。

（三） 利用氯化銦催化環己烯炔-炔醯胺化合物進行分子內環化反應，得到γ-內醯胺化合物。此反應推測會形成帶有keteniminium的中間體後得到γ-內醯胺化合物。此反應的優點為條件溫和、操作簡單，起始物的製備也相當容易。

Lewis acid-promoted cyclization reactions of cyclic six-membered ring 1-yne-ynamides , ynamide-tethered furans and cyclohexene-yne-ynamides afforded spiro[3.5]nonanes, pyrroles and γ-lactams, respectively. （1）The iron(III) bromide-promoted cyclization of six-membered ring 1-yne-ynamides provided brominated spiro[3.5]nonane derivatives. The reaction mechanism was suggested to proceed via a N- to C- allyl transfer followed by aza-Prins cyclization generated spiro[3.5]nonane derivatives. The reaction had several advantages: inexpensive iron (III) bromide and short reaction times.Imines were also formed via a cumulenen intermediate followed by [2 + 2] cyclization.

（2）The gold(III) chloride-catalyzed intramolecular cyclization reaction of ynamide-tethered furans afforded 3-aryl-substituted-4-(3-oxopropen-1-yl)pyrroles in good yields. The advantages of this reaction are mild reaction conditions and short reaction times.

（3）The indium(III) chloride-promoted intramolecular cyclization of alkyl or aryl-substituted cyclohexene-yne-ynamides under nitrogen afforded γ-lactams. The reaction mechanism was suggested to proceed via a keteniminium intermediate, generating γ-lactams. The advantages of this reaction are operationally simple, mild reaction conditions and easily available of starting materials.