第一章
經由自由基加成反應，以烯烴與添普調控所單離出之苯胺基丁烯酮基質（(E)-4-(phenylamino)-4-((2,2,6,6-tetramethylpiperidin-1-yl)oxy) prop-3-en-1-substituted -2-one）在搭配0.03當量的樟腦磺酸、加熱至120°C的氮氣環境下進行加成，在此條件下，可得到高產率的苯基胺二酮形式的產物（2-substituted-3-oxo-N-phenylbutanamide）。
除此之外，本反應更可與前一步驟之分子內氧化反應進行一鍋化反應，產率也大多能夠維持有一定的水準（50%-70%）。
第二章
本章記錄利用無金屬催化的自由基加成環化反應來進行1-烯丙基-2-乙烯基苯與亞硝基苯的環化，利用亞硝基苯的自由基活性來促使1-烯丙基-2-乙烯基苯這種類型的雙烯化合物進行[2+2+2]的環化，建構出一系列氮氧雜環之結構產物2-苯基代-2,3,3a,4,9,9a-六氫萘並[2,3-d]異噁唑（2-phenyl-2,3,3a,4,9,9a-hexahydronaphtho[2,3-d]isoxazole），這種新的環加成反應是目前少數是使用烯烴來進行[2+2+2]合環反應的例子，而本篇討論之反應可以在不添加溶劑之氮氣環境下，加熱至120°C成功產生出理想產物。

PART 1
Here, we described the synthesis of 2-substituted-3-oxo-N-phenylbutanamide through an efficient radical addition reaction. Optimizing the condition for the radical addition of alkenes with (E)-4-(phenylamino)-4-((2,2,6,6-tetramethylpiperidin-1-yl)oxy) prop-3-en-1-substituted-2-one, and we have it best performed at 120 oC in toluene that described with moderate to good yields. The structures of products consist of diketone and N-phenylamide, which could be used for further applications such as providing starting materials for Mannich reaction to synthesize natural products.

PART 2

This part of the dissertation deals with a metal free [2+2+2] radical cycloaddition of 1-allyl-2-vinylbenzene derivatives and nitrosobenzenes constructing (1S,4S)-2-phenyl-2,3,4,5-tetrahydro-1H-4,1-(epoxymethano) benzo[c]azepine derivatives. The advantages of this new radical cycloaddition are based on the easily accessible substrates and the readily achievable condition. There are only few examples using alkene for [2+2+2] radical cycloaddition reactions so far, which highlighted the value of this research.

目錄
謝誌 I
中文摘要 II
中文摘要 III
英文摘要 IV
目錄 V
表目錄 VIII
圖目錄 IX
附件目錄 XI
英文縮寫對照表 XVII
第一章 2
第一節 緒論 2
第二節 文獻回顧 3
2-1 銅金屬催化自由基氧化環化反應 3
2-2長效自由基化合物 4
2-3 以過度金屬催化之自由基反應 5
2-4 無金屬催化之自由基反應 6
2-5以氮氧化合物調節自由基加成反應 7
2-6無金屬之異羥肟酸類型自由基反應 8
2-7以添普調節自由基加成環化反應 9
2-8反應應用 11
第三節 實驗目標與動機 12
3-1實驗動機與新方法 12
3-2 苯胺基丁烯酮與未活化烯烴進行自由基加成反應 13
3-3 最佳化反應條件 14
3-4基質合成 17
3-5 多種苯胺基烯酮與正辛烯進行自由基加成反應的容忍度測試 17
3-6 苯胺基丁烯酮與多種烯類進行自由基加成反應的容忍度測試 19
3-7 反應一鍋化之測試 23
3-8 反應機構探討 25
3-7 N-苯基碳酰胺應用 26
3-8 結構鑑定 27
第四節 結論 36
第五節 實驗部分 36
5-1 實驗的一般操作 36
5-2 基質合成 39
5-3 催化步驟 46
5-4 實驗光譜數據資料 47
第六節 參考文獻 64
第二章 126
第一節 緒論 126
第二節 文獻回顧 127
2-1前言 127
2-2分子內雙烯自由基環化反應 127
2-3 亞硝基苯之性質與應用 128
2-4 亞硝基化合物之短週期自由基效應 129
2-5 N-苯基羥胺與亞硝基化合物之銅催化含氧氧化反應 130
2-6銅金屬調節芳香亞硝基化合物與3-N-羥基烯丙胺之[3+2]環化反應 131
第三節 結果與討論 132
3-1實驗動機與構思 132
3-2 1-烯丙基-2-乙烯基苯與亞硝基苯反應合環 132
3-3 最佳化反應條件-1 133
3-4最佳化反應條件-2 135
3-5 基質合成 136
3-6 反應機構推論 137
3-7 結構鑑定 139
第四節 結論 148
第五節 實驗部分 148
5-1 實驗的一般操作 148
5-2 基質合成 151
5-3 自由基加成步驟 154
5-4 實驗光譜數據資料 154
第六節 參考文獻 159

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