銅催化碳硫偶合反應之陽離子效應研究;The cation effect of copper catalyzed C-S coupling study

Please use this identifier to cite or link to this item: http://ir.lib.ncu.edu.tw/handle/987654321/54112

Title:	銅催化碳硫偶合反應之陽離子效應研究;The cation effect of copper catalyzed C-S coupling study
Authors:	張原銘;Chang,Yuan-ming
Contributors:	化學研究所
Keywords:	碳硫偶合反應;銅催化;Copper catalyzed;C-S coupling
Date:	2012-07-12
Issue Date:	2012-09-11 18:36:37 (UTC+8)
Publisher:	國立中央大學
Abstract:	以銅(I)催化劑進行偶合反應生成碳-硫鍵，一直以來被廣泛應用於有機合成、天然物藥物合成。通常是在含有鹵化銅、配位基和鹼類的反應。在這篇論文中，我們發現在此催化系統中之反應性受到不同鹼金族陽離子以及配位基的影響。因此，我們猜測其反應途徑可能會先形成[Cu(SPh)2]一和 Cu(SPh)的平衡，再進行氧化加成作用。目前尚未直接的分離或直接觀察出催化系統下的中間產物。因此我們藉由in situ ESI-MS高溫下觀測到[Cu(SPh)2]一、配位基抓住鹼金族陽離子等的訊號，進而推測其反應性是受到鹼(鹼金族陽離子)的影響。而s K-edge X- ray 吸收光譜也可以定性地解釋不同的鹼(鹼金族陽離子)如何影響碳硫偶合的反應性，並說明配位基在催化系統中所扮演的角色。The reactions of copper(Ⅰ)-catalyzed cross-coupling C-S bond formation have been widely used in organic synthesis, the synthesis of natural products and pharmaceuticals. The common methods for the C-S coupling require copper, base, and ligands. In this thesis, the reaction of thiophenol and iodobenzene forms diaryl sulfides were affected by metal cation and ligands.Therefore, we proposed the equilibrium between [Cu(SPh)2]一 and Cu(SPh) before going to oxidative additive reaction. However, the direct isolation or observation of intermediates can not be achieved. Thus, we used in situ ESI-MS to find out the intermediates of catalytic reaction. We observed [Cu(SPh)2]一 and alkali metal cations trapped by ligands in reaction solutions. Moreover, the sulfur K-edge X-ray absorption spectrum could qualitatively explain how the different bases(cations) affect the catalytic system and why ligands could enhance the reactivity of this catalytic system.
Appears in Collections:	[Graduate Institute of Chemistry] Electronic Thesis & Dissertation

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