銅(I)催化的碳硫偶合反應中間產物研究; Intermediates of Copper(I)-Catalyzed C-S Cross Coupling study

Please use this identifier to cite or link to this item: http://ir.lib.ncu.edu.tw/handle/987654321/48016

Title:	銅(I)催化的碳硫偶合反應中間產物研究;Intermediates of Copper(I)-Catalyzed C-S Cross Coupling study
Authors:	鄭韶文;Shao-Wen Cheng
Contributors:	化學研究所
Keywords:	偶合反應;電灑式游離法質譜儀;銅催化;碳硫鍵;ESI-MS;cross coupling;C-S bond;copper-catalyzed
Date:	2011-07-14
Issue Date:	2012-01-05 14:27:15 (UTC+8)
Abstract:	以銅(I)催化劑進行偶合反應生成碳-硫鍵，一直以來被廣泛的應用在有機合成、天然物及藥物合成，通常是在含有鹵化銅、配位基和鹼類的反應系統中進行。近年來，對於各式各樣的催化條件的反應機構產生極大興趣，以碘化銅-二氮雜菲-叔丁醇鉀的反應系統中，在120 ℃下將苯硫酚和碘化苯進行偶合反應，生成二芳基硫化物，而該反應是在120 ℃下進行。由於在銅催化之碳-硫鍵生成反應中，目前尚未直接的分離或直接觀察出在催化系統下的中間產物，而且銅催化反應的反應機構目前尚未被確立。因此我們藉由in situ ESI-MS來測試其催化反應，繼而於高溫條件下測得溶液中含有[Cu(SPh)2]－、[Cu(SPh)I]－和K[Cu(SPh)2(Ph)]+，推測其為反應的中間產物，經由觀察到的這些中間產物推其反應機構，因此優化催化條件以提升反應性。 The reactions of copper(I)-catalyzed cross-coupling C-S bond formation have been widely used in organic synthesis, synthesis of natural products and pharmaceuticals. The common methods for the formation of C-S bonds often require copper salts, ligand and base. Recently, the mechanism of a large variety catalytic conditions became more interested. In this thesis, the reaction of the thiophenol and iodobenzene coupling reaction of diaryl sulfides in copper iodide- phenanthroline-potassium tert-butoxide at 120 ℃ was studied. The direct isolation or observation of intermediates from the copper catalytic cannot be achieved. Moreover, the mechanism of copper catalyst reaction has not been understood. Therefore, we used in situ ESI-MS to characterize the intermediates of catalytic reaction at high temperature. We observed [Cu(SPh)2]－,[Cu(SPh)I]－and K[Cu(SPh)2(Ph)]+ in reaction solution. Based on these observations, a catalytic cycle is proposed. We optimized the reaction conditions to improve our reactivities.
Appears in Collections:	[Graduate Institute of Chemistry] Electronic Thesis & Dissertation

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