請用此 Handle URI 來引用此文件: http://hdl.handle.net/11455/16833
標題: 1.三氯化鐵在碳-硫鍵交互耦合反應上的應用 2.高效率銅催化炔類與芳香基碘化物之耦合反應
1. Applications of Iron(III) Chloride in C-S Bond Cross-Coupling Reactions 2. Efficient Copper-Catalyzed Cross-Coupling Reaction of Alkynes with Aryl Iodides
作者: 林哲弘
Lin, Che-Hung
關鍵字: Iron-Catalyzed
鐵催化
Cross-Coupling
Copper-Catalyzed
Sonogashira Reaction
耦合反應
碳硫鍵
銅催化
Sonogashira反應
出版社: 化學系所
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摘要: 過渡金屬催化交互耦合反應在現今已經成為一個重要的方法來合成碳-碳、碳-雜原子鍵。過去的研究主要著重在鈀、鎳、鈷等昂貴且對環境有害的金屬。在此,本研究使用便宜、低毒性且環保的鐵金屬來進行碳-硫鍵交互耦合反應。使用三氯化鐵/雙螯合磷配位基(Xantphos)作為催化劑,針對文獻中反應性較差的烷基硫醇來測試反應,除了對各種芳香基碘化物都有不錯的產率,這也是首次使用鐵金屬將烷基硫醇進行碳-硫鍵交互耦合反應的例子。 Sonogashira反應是目前最常被使用來合成炔類化合物的方法。然而,傳統上必須使用到鈀與銅或是鈀金屬才能進行這類型的反應,近年來漸漸的轉向使用較便宜且低毒性的銅金屬,但大多需要使用到5-10 mol%或更高的銅與配位基。本實驗研究出使用1 mol%的Cu2O與(1 mol%) Xantphos就可以成功的進行反應,對於各種官能基與高立體障礙基團取代的化合物,都有非常高的產率。
The transition-metal-catalyzed cross-coupling reaction is one of the most powerful strategies for constructing carbon-carbon and carbon-heteroatom bonds. During the last decades, manifold transition metal catalysts especially based on precious metals such as palladium, nickel, and cobalt. Herein we report that iron can be used as a cheap, nontoxic and environmentally friendly metal. The combination of iron trichloride with Xantphos is a very active system for coupling reaction of alkyl thiols with a variety of aryl thiols for the first time. Sonogashira reaction is probably the most popular strategies for the syntheses of functionalized alkynes from aryl halides and terminal alkynes. The vast majority of the existing protocols involve the use of palladium catalyst. Recent years, copper-catalyzed Sonogashira reaction has gained much attention due to the lower cost of copper salts. However, among the known procedures, 5-10 mol% or higher copper salts are generally required along with high loading of ligands. The second part of this thesis, we describe the combination of Cu2O (1.0 mol%) with Xantphos (1.0 mol%) is a powerful system for this transformation. A broad spectrum of functional groups can be tolerated during the catalysis.
URI: http://hdl.handle.net/11455/16833
其他識別: U0005-2807201016410500
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