臺灣博碩士論文加值系統

炔類和烯炔類化合物是有機合成，材料科學和製藥工業中的重要骨架。近年來，利用過渡金屬催化末端炔烴與鹵芳烴和乙烯基鹵化物之耦合反應是合成此類化合物的重要方法。其中Sonogashira反應採用鈀和銅金屬共催化是最後歡迎的方法之一; 然而由於鈀金屬毒性高且昂貴，近年來利用便宜的金屬催化的Sonogashira類型反應吸引了許多科學家參與研究。本論文的第一部分，我們發現銅錯合物CuI(xantphos) 1.0–5.0 mol %可以有效地促進末端炔類與乙烯基鹵烷跟芳香基鹵化物進行耦合反應; 另一方面，我們發現用Cu2O當催化劑、DMF當溶劑可以在不需要配體的反應條件下成功的完成此類型反應。
在本論文第二部分，我們發現錳金屬可以催化sonogashira反應，初步結果發現二氯化錳搭配1,10-菲繞啉為配體，可以有效地促進炔類和芳香基碘化物之交互耦合反應。

Alkynes and enynes are important function group in organic synthesis, materials science and pharmaceutical industry. The transition-metal-catalyzed coupling reaction of terminal alkynes with aryl halides and vinyl halides are attractive methods for preparing alkynes and enynes. More recently, the exclusive use of copper, as catalyst has gained significant attention in the Sonogashira-type reaction owing to the low cost of copper salts. Typically, the combination of palladium and copper as catalyst is quite popular. However, palladium is highly toxic and expensive. In the first part of this thesis we reported that:
I. CuI(xantphos) is an active catalyst for the synthesis of enynes;
II. The copper-catalyzed Sonogashira-type reaction can be perfomed under ligand-free condition.
The second part of this thsis, we report the combination of MnCl2 with 1, 10 – phenanthroline is an active catalytic system for coupling reation of terminal alkynes with aryl iodides. To the best of our knowledge, this is the first manganese-catatyzed Sonogashira-type couplong reaction.

摘 要....................................i
Abstract.................................ii
一、 序論..............................1
(一) 過渡金屬之交互耦合反應...............1
(二) Sonogashira類型耦合反應............4
二、 研究動機.........................16
(一) 銅金屬催化Sonogashira類型耦合反應... 16
(二) 錳催化Sonogashira類型耦合反應......17
三、 結果與討論.......................18
(一) 銅金屬催化Sonogashira類型反應......18
I. 高效率銅催化乙烯基鹵烷和炔類耦合反應..18
II. 氧化亞銅催化芳香基碘苯和炔類耦合反應..26
(二) 錳金屬催化Sonogashira類型反應......33
四、 結論與展望.......................40
五、 儀器設備與藥品溶劑.................41
(一) 儀器設備............................41
(二) 藥品溶劑............................40
六、 實驗步驟.........................43
七、 光譜數據.........................46
八、 參考資料........................114
九、 NMR光譜........................117

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