第一章

經由有效的鋅催化劑，將中端炔和Chloramine-T在室溫下進行氯胺化，在溫和的條件下，得到高產率的雙氯亞胺形式的產物（(Z)-2,2-dichloro-N-methyl-N-(methylsulfonyl)-2-phenyl-N'-tosylacetimidamide），產物還具備的兩個缺電子基團，容易與其他不同的親核試劑進行下一步反應。

第二章

利用金金屬催化劑，催化兩個末端炔醯胺和烯類進行立體選擇性[2+2+2]-環加成反應，建構出多取代苯環的衍生物，這種新的環加成反應的效用適用在廣泛範圍的炔醯胺和乙烯基乙醚或2-甲氧基丙烯有優異的區域選擇性與表現，且目前較少例子是使用烯烴，來進行[2+2+2]合環反應。

PART 1

The synthesis of (Z)-2,2-dichloro-N-methyl-N-(methyl-sulfonyl) -2-phenyl-N'-tosylacetimidamide, an efficient zinc catalyzed reaction enhancing the reactivity for the chloroamination of alkynes with Chloramine-T at room temperature, is described with moderate to good yields. The electron-deficient character of the azomethine group of polyhalogenaldimines promotes their interactions with numerous nucleophiles, which could be used for further reactions.



PART 2

This part of the dissertation deals with the gold-catalyzed regiocontrolled [2+2+2]cycloadditions of two ynamides and vinyl ether constructing polysubstituted benzene derivatives. The utility of this new cycloaddition is manifested in the excellent regioselectivity with a wide range of scope of applicable ynamides as well as vinyl ether. And there are few examples using alkene for [2+2+2]cyclization reactions.

謝誌 I
目錄 II
中文摘要 VI
中文摘要 VII
英文摘要 VIII
表目錄 IX
圖目錄 X
附件目錄 XII
英文縮寫對照表 XVII
第一節 緒論......1
第二節 文獻回顧......2
2-1 過渡金屬催化進行氯胺化加成反應......2
2-2多氯亞胺的合成 ......3
2-3 藉由金剛烷和超強酸下來還原 N-（聚氯乙烯）- 和N-（1-羥基聚氯乙基）芳烴磺胺類藥物......3
2-4 銅催化(E)-b-chloro-enesulfonamides的合成......4
2-5多氯亞胺的應用 ......5
第三節 實驗目標與動機......8
3-1實驗動機與新方法......8
3-2 炔醯胺與Chloramine-T反應進行氯胺化（chloroamination）......9
3-3 最佳化反應條件......11
3-4基質合成......12
3-5 鋅催化多種炔醯胺與Chloramine-T進行氯胺化加成反應的範圍...... 13
3-6 反應機構探討 ......16
3-7 雙氯亞胺應用 ......18
3-8 結構鑑定 ......21
第四節 結論 ......25
第五節 實驗部分 ......25
5-1 實驗的一般操作......25
5-2 基質合成 ......27
5-3 催化步驟 ......38
5-4 實驗光譜數據資料......39
第六節 參考文獻 ......49
第二章......95
第一節 緒論......95
第二節 文獻回顧......96
2-1過渡金屬催化[2+2+2]環加成反應......96
2-2過渡金屬鎳和鋁催化的多取代苯環合成......97
2-3 藉由鎳催化二氧化碳和雙炔進行[2+2+2]-環加成pyrones合成...... 98
2-4 銥催化雙炔和正丁基乙烯基醚進行[2+2+2]環加成......99
2-5過渡金屬鎳催化進行二氫萘合成......100
2-6金催化Ynamides和烯烴進行分子間的[4+2] 和 [2+2+2]合環...... 101
2-7金催化炔醯胺和兩分子腈進行分子間的 [2+2+2]合環......102
2-8金催化兩分子炔醯胺和腈進行分子間的2+2+2]合環......102
第三節 結果與討論......103
3-1實驗動機與構思......103
3-2 炔酰胺與乙烯基乙醚反應進行[2 + 2 +2]合環......104
3-3 最佳化反應條件......105
3-4基質合成......107
3-5 金催化多種末端炔醯胺與乙烯基乙醚進行{2+2+2}-環加成反應的範圍......108
3-6　金催化末端炔醯胺與2-甲氧基丙烯進行{2+2+2}環加成反應的範圍...... 111
3-7 反應機構探討 ......112
3-8 結構鑑定 ......114
第四節 結論 ......116
第五節 實驗部分 ......116
5-1 實驗的一般操作......116
5-2 基質合成 ......119
5-3 催化步驟 ......122
5-4 實驗光譜數據資料......124
第六節 參考文獻 ......135

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