壹、beta-硝基苯乙烯的應用—4-芳基四氫異喹啉、3-芳基吲哚、2-芐基苯並呋喃及2-芳基色滿衍生物的合成 貳、茚並異喹啉的合成
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2017
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本論文分為兩個章節，每章節各自獨立，包含前言、研究目標、實驗結果
與討論，以及結論。
第壹章節探討beta-硝基苯乙烯衍生物在化學合成上的發展性與應用性，可以分為四個部分，分別為4-芳基四氫異喹啉、3-芳基吲哚、2-芐基苯並呋喃及2-芳基色滿四種化合物的合成。第一部分，beta-硝基苯乙烯與芳環用三氯化鋁催化傅-克烷化反應合成硝基烷，其還原後的胺類以傅-克反應或皮克特-施彭格勒反應得到4-芳基四氫異喹啉衍生物；若將胺類以銅試劑催化烏爾曼反應則是新穎的3-芳基吲哚合成法，為第二部分。第三部分，將beta-硝基苯乙烯衍生物還原為硝基烷，經過內夫反應合環得到2-苄基苯並呋喃；第四部份則將硝基烯衍生物作為中間產物，在鹼催化下一鍋化合成2-芳基色滿。
第貳章節為茚並異喹啉的合成，分成三個部分，第一部分以2-碘苯甲醯胺與茚滿二酮為起始物，在乙腈中銅催環化反應得到茚並異喹啉衍生物。第二部分為第一部分的反應條件的改良，除了將溶劑改為水，也縮短了反應時間跟減少銅試劑的使用量。第三部分為茚並異喹啉的合成展望，嘗試由2-鹵苯甲酸與茚滿二酮作為起始物，在反應過程中加入胺類以一鍋化合成茚並異喹啉衍生物，可減少合成步驟並提升原子效益。
The content of the thesis is divided into two chapters, each chapter individually including preface, research goal, results and discussions, and conclusion. Chapter I discuss about the applicability of beta-nitrostyrene derivatives for the synthesis of four types of structurally different compounds such as 4-aryltetrahydroisoquinoline, 3-arylindole, 2-benzylbenzofuran and 2-arylchroman derivatives. This chapter is divided into four parts. In the first part, the amines derived from nitroalkanes, which was synthesized via AlCl3-catalyzed Friedel-Crafts alkylation and reductive amination of beta-nitrostyrenes and arenes, underwent Friedel-Crafts cyclization or Pictet-Spengler reaction to produce 4-aryltetrahydroisoquinolines. In the second part, the amines were treated with copper catalyst to furnish 3-arylindoles. For third and fourth parts, nitroalkene derivatives modified from beta-nitrostyrenes were subjected to Nef reaction to yield 2-benzylbenzofurans, or treated with base to do Michael addition to obtain 2-arylchroman derivatives. Chapter II is the synthesis of indenoisoquinolines, and is divided into three parts. The first part using 2-iodobenzamides and 1,3-indandiones as starting materials, which were transformed into indenoisoquinoline derivatives by copper-catalyzed cyclization in acetonitrile . The second part deals with the water-mediated synthesis of the same compounds under reduced amount of copper catalyst. The third part is a progressive project. We replaced 2-iodobenzamides with 2-halobenzoic acids as starting materials, after coupling with 1,3-indandione the amine derivative could be inserted and cyclized to afford the desired indenoisoquinolines. This one-pot water-mediated synthesis can save synthetic steps and improve atom efficiency.
The content of the thesis is divided into two chapters, each chapter individually including preface, research goal, results and discussions, and conclusion. Chapter I discuss about the applicability of beta-nitrostyrene derivatives for the synthesis of four types of structurally different compounds such as 4-aryltetrahydroisoquinoline, 3-arylindole, 2-benzylbenzofuran and 2-arylchroman derivatives. This chapter is divided into four parts. In the first part, the amines derived from nitroalkanes, which was synthesized via AlCl3-catalyzed Friedel-Crafts alkylation and reductive amination of beta-nitrostyrenes and arenes, underwent Friedel-Crafts cyclization or Pictet-Spengler reaction to produce 4-aryltetrahydroisoquinolines. In the second part, the amines were treated with copper catalyst to furnish 3-arylindoles. For third and fourth parts, nitroalkene derivatives modified from beta-nitrostyrenes were subjected to Nef reaction to yield 2-benzylbenzofurans, or treated with base to do Michael addition to obtain 2-arylchroman derivatives. Chapter II is the synthesis of indenoisoquinolines, and is divided into three parts. The first part using 2-iodobenzamides and 1,3-indandiones as starting materials, which were transformed into indenoisoquinoline derivatives by copper-catalyzed cyclization in acetonitrile . The second part deals with the water-mediated synthesis of the same compounds under reduced amount of copper catalyst. The third part is a progressive project. We replaced 2-iodobenzamides with 2-halobenzoic acids as starting materials, after coupling with 1,3-indandione the amine derivative could be inserted and cyclized to afford the desired indenoisoquinolines. This one-pot water-mediated synthesis can save synthetic steps and improve atom efficiency.
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4-芳基四氫異喹啉, 3-芳基吲哚, 2-苄基苯並呋喃, 2-芳基色滿, 茚並異喹啉, 3-aryltetrahydroisoquinoline, 3-arylindole, 2-benzylbenzofuran, 2-arylchroman, indenoisoquinoline