利用銅催化劑進行芳鹵化物與硫粉之碳硫耦合反應:合成策略與機制探討

C-S coupling Reaction of Arylhalide and Sulfur Utiling Copper-catalyzed System:Synthesis Strategies and Mechanism Study.

彭維德(Wei-Te Peng)

指導教授 ： 陳喧應

高雄醫學大學/生命科學院/醫藥暨應用化學研究所/碩士(2012年)

摘要

近年來，碳硫耦合反應倍受科學家關注，是因為藥物中若含有硫原子可提升藥物的生物活性。曾有文獻提出，將硫粉和芳香鹵化物以碘化亞銅進行耦合反應，其產物只有二環二硫醚。但在本研究發現，以硫粉為原料的碳硫耦合反應使用不同種的鹼塩，卻出現兩種產物分別為二環二硫醚與二環硫醚化合物。此實驗中發現，可利用調控鹼性的強度，可獲得不同比例的二環二硫醚與二環硫醚化合物。因此，我們提出合成不對稱的二異環硫醚化合物的新合成策略：第一步利用硫粉與芳香鹵化物以碘化亞銅並搭配特定的鹼鹽，將可得到二環二硫醚化合物。第二步再將二環二硫醚與另一種芳香鹵化物以碘化亞銅搭配鹼鹽即可獲得不對稱之二異環硫醚產物。實驗以一系列芳香鹵化物作為第二步之原料，實驗並證明此合成策略之可行性。此外，我們也將嘗試外加一系列配位基探討對碳硫耦合反應的影響，並合成銅錯合物來確定催化劑的結構與型態。

關鍵字

耦合反應 ； 碘化亞銅 ； 雙芳香環硫醚 ； 雙芳香環二硫醚

並列摘要

Recently scientists pay attention to C-S coupling reaction because of their derivatives with biological activity. The literature reported that the S-arylation products were diaryl disulfane if the precursors of were sulfur powder and aryl halide using CuI as the catalyst. But our research showed that diaryl sulfane and diaryl disulfane are the co-products if different bases were used for the above S-arylation. And the ratio of two products could be controlled by the basicity of the bases. Moreover, we proposed the new strategy of unsymmetrical diaryl sulfane synthesis form sulfur powder and aryl halide that diaryl disulfane is synthesized by specific base first and then reacted with another aryl halide to produce using CuI as the catalyst. Various aryl halides were tested to synthesize diaryl sulfane and diaryl disulfane for proving the feasibility of this new strategy. Eventally, it was taken the try-out for various ligands seriously and synthesized their Cu complexes to improve this catalytic reaction.

並列關鍵字

Coupling reaction ； copper iodide ； diaryl sulfane ； diaryl disulfand

參考文獻

參考文獻 :

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