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研究生： 蔡安益
Tsai, An-I
論文名稱： 金屬離子起始氧化性自由基反應在-1,4-醌類及雜環化合物的研究
Metal ions mediated oxidative free radical reactions of 1,4-quinones and heterocycles
指導教授： 莊治平
Chuang, Che-Ping
學位類別： 博士
Doctor
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2008
畢業學年度： 96
語文別： 中文
論文頁數： 186
中文關鍵詞： 自由基 、吡咯化合物 、吲哚化合物 、硝酸銀(I) 、醌類化合物 、硝酸鈰銨(IV) 、醋酸錳(III)
外文關鍵詞： Cerium (IV), Silver(I), indoles, Manganese(III), free radical, pyrroles
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    • 數十年來，自由基在有機合成的運用越來越受到重視。其中自由基形成碳-碳鍵的方法尤其重要，化學家已習慣將其視為合成複雜化合物的一項策略。
    由R3SnH將鹵素或其他官能基生成自由基，並經由環化以及還原等連鎖反應將自由基生成碳氫化合物，為一種典型、廣泛使用的自由基環化反應。雖然此類型反應具有良好的產率，但由於產物並不具有官能基化導致應用受到限制。氧化性自由基的環化反應通常伴隨著自由基的氧化或環化後自由基的氧化，可將簡單的起始物導入官能基化的產物，因此具有很好的合成潛力。
    本論文主要探討如下:
    (1)1,4-醌類衍生物與酮基化合物、苯甲醯乙腈化合物、β-烯胺羰基化合物、羧酸化合物、β-雙羰基化合物的氧化性自由基反應。
    碳自由基可經由金屬氧化酮類、β-烯胺羰基或β-雙羰基化合物有效產生，並與1,4-醌類化合物進行分子間的自由基加成反應形成spirolactam、indole-4,7-dione 或 isobenzofuran-4,7-dione等化合物。
    (2)吲哚化合物與β-雙羰基化合物的氧化性自由基反應。
    β-雙羰基化合物經由錳(III)氧化所生成的自由基也可以有效加成至3位上無取代吲哚的2位上，並生成2-(3-oxo-2-indolylidene)malonates或furo[3,2-b] indoles化合物。
    (3)β-胺基肉桂酸酯的氧化性自由基反應。
    經由β-胺基肉桂酸酯與烯胺化合物的氧化性自由基反應，合成出多取代的吡咯化合物。

    The use of radicals in organic synthesis has increased dramatically within the last decades. Radical carbon-carbon bond-forming reactions have grown in importance to the point where chemists are now routinely considered in strategy planning of complex targets.
    A typical, widely used radical cyclization involves the reduction of a halide or other functional group to a radical with R3SnH, followed by cyclization and reduction of the resulting radical to a hydrocarbon in the chain propagation steps. While this sequence often gives high yields of products, this approach is limited, leading to relatively unfunctionalized products. Oxidative free-radical reaction in which the initial radical is generated oxidatively or the cyclic radical is terminated oxidatively, has considerable synthetic potential, since more highly functionalized products can be prepared from simple precursors.
    In this report, we describe our results on:
    (1) Oxidative free radical reactions between 1,4-quinone derivatives and ketones, benzoylacetonitriles, β-enamino ketones, carboxylic acids, β- dicarbonyl compounds.
    Carbon radicals which can be generated effectively by metal ion oxidation of ketones,β-enamino ketones orβ-dicarbonyl compounds undergo inter- molecular free radical additions with 1,4-quinones to produce spirolactam, indole-4,7-dione or isobenzofuran-4,7-dione.
    (2) Oxidative free radical reactions between indole derivatives and β- dicarbonyl compounds.
    Radical generated by the manganese(III) oxidation ofβ-dicarbonyl compounds undergoes efficient addition to the 2-position of 3-unsubstituted indoles and 2-(3-oxo-2-indolylidene)malonates or furo[3,2-b] indoles was produced.
    (3) Oxidative free radical reactions of β-aminocinnamates.
    We describe an effective method for the synthesis of highly substituted pyrroles via oxidative free radical reaction betweenβ-aminocinnamates and enamines.

    第一章 前言 .............................................................................................. 1 第一節 自由基的性質 .................................................................................. 1 一. 自由基的前列分子軌域理論 .......................................................... 1 二. 自由基的生成方式 .......................................................................... 4 三. 自由基的環合及重排反應 .............................................................. 5 第二節 氧化性自由基反應 ........................................................................ 14 一. 錳(III)的氧化性自由基反應 ......................................................... 15 二. 鈰(IV)的氧化性自由基反應 ......................................................... 17 三. 銀(II)的氧化性自由基反應 ........................................................... 18 參考資料 ...................................................................................................... 21 圖一 ................................................................................................................ 2 圖二 ................................................................................................................ 2 圖三 ................................................................................................................ 9 圖四 ................................................................................................................ 9 流程一 ............................................................................................................ 2 流程二 ............................................................................................................ 3 流程三 ............................................................................................................ 6 流程四 ............................................................................................................ 8 流程五 .......................................................................................................... 10 流程六 .......................................................................................................... 10 流程七 .......................................................................................................... 11 流程八 .......................................................................................................... 12 流程九 .......................................................................................................... 14 流程十 .......................................................................................................... 15 流程十一 ...................................................................................................... 16 流程十二 ...................................................................................................... 16 流程十三 ...................................................................................................... 18 流程十四 ...................................................................................................... 19 流程十五 ...................................................................................................... 19 第二章 1,4-醌類化合物的氧化性自由基反應 .............................. 24 第一節 簡介 ................................................................................................ 24 第二節2-甲胺基-1,4-醌類化合物與α-氯-β-雙羰基化合物的氧化性自由基反應 ........................................................................................ 28 第三節 2-烷胺基-1,4-醌類化合物與羰基化合物的氧化性自由基反應 …………………………………………….………………............. 32 第四節 2-羥基-1,4-萘醌類化合物與β-烯胺羰基化合物的氧化性自由基反應 ................................................................................................ 42 第五節 利用1,4-萘醌類化合物的自由基反應，合成出異呋喃-1,4-醌類化合物 ................................................................................................ 46 實驗部分 ...................................................................................................... 57 第二節 …….................................................................................................. 57 第三節 …….................................................................................................. 61 第四節 …….................................................................................................. 73 第五節 …….................................................................................................. 76 參考資料 ...................................................................................................... 87 各類型反應之典型1H, 13C NMR光譜資料 ................................................ 89 表一 .............................................................................................................. 28 表二 .............................................................................................................. 29 表三 .............................................................................................................. 31 表四 .............................................................................................................. 33 表五 .............................................................................................................. 34 表六 .............................................................................................................. 36 表七 .............................................................................................................. 37 表八 .............................................................................................................. 39 表九 .............................................................................................................. 41 表十 .............................................................................................................. 42 表十一 .......................................................................................................... 44 表十二 .......................................................................................................... 48 表十三 .......................................................................................................... 49 表十四 .......................................................................................................... 49 表十五 .......................................................................................................... 50 表十六 .......................................................................................................... 52 表十七 .......................................................................................................... 54 表十八 .......................................................................................................... 54 流程一 .......................................................................................................... 25 流程二 .......................................................................................................... 25 流程三 .......................................................................................................... 26 流程四 .......................................................................................................... 27 流程五 .......................................................................................................... 30 流程六 .......................................................................................................... 33 流程七 .......................................................................................................... 35 流程八 .......................................................................................................... 40 流程九 .......................................................................................................... 43 流程十 .......................................................................................................... 46 流程十一 ...................................................................................................... 47 流程十二 ...................................................................................................... 51 流程十三 ...................................................................................................... 52 流程十四 ...................................................................................................... 55 流程十五 ...................................................................................................... 55 第三章 吲哚化合物的氧化性自由基反應 .................................... 118 第一節 簡介 .............................................................................................. 118 第二節 吲哚化合物與β-雙羰基化合物的氧化性自由基反應 …........ 126 實驗部分 .................................................................................................... 135 參考資料 .................................................................................................... 143 各類型反應之典型1H, 13C NMR光譜資料 .............................................. 144 表一 ............................................................................................................ 127 表二 ............................................................................................................ 127 表三 ............................................................................................................ 128 表四 ............................................................................................................ 130 表五 ............................................................................................................ 133 流程一 ........................................................................................................ 118 流程二 ........................................................................................................ 119 流程三 ........................................................................................................ 120 流程四 ........................................................................................................ 120 流程五 ........................................................................................................ 121 流程六 ........................................................................................................ 122 流程七 ........................................................................................................ 123 流程八 ........................................................................................................ 123 流程九 ........................................................................................................ 125 流程十 ........................................................................................................ 129 流程十一 .................................................................................................... 132 流程十二 .................................................................................................... 134 第四章 β-胺基肉桂酸酯的氧化性自由基反應 ......................... 152 第一節 簡介 .............................................................................................. 152 第二節 β-胺基肉桂酸酯與β-烯胺基羰基化合物的氧化性自由基反應 ........................................................................................................ 158 實驗部分 .................................................................................................... 167 參考資料 .................................................................................................... 177 各類型反應之典型1H, 13C NMR光譜資料 .............................................. 178 表一 ............................................................................................................ 155 表二 ............................................................................................................ 159 表三 ............................................................................................................ 160 表四 ............................................................................................................ 161 表五 ............................................................................................................ 163 表六 ............................................................................................................ 164 表七 ............................................................................................................ 165 表八 …........................................................................................................ 166 流程一 ........................................................................................................ 152 流程二 ........................................................................................................ 153 流程三 ........................................................................................................ 154 流程四 ........................................................................................................ 155 流程五 ........................................................................................................ 157 流程六 ........................................................................................................ 160 流程七 ........................................................................................................ 164

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