臺灣博碩士論文加值系統

本研究製備出以1,2-環己二胺以及鄰苯二胺為架構的雙氮配位基(3a-3h)，並且進一步反應形成二級氧化膦基(SPOs)(4a-4c)。成功利用X-ray單晶繞射法鑑定分子4c和錯合物3a_Pd、3b_Pd、3c_Pd以及3d_Cu等結構。在配位基的優選過後，發現雙氮配位基對於鈀金屬具有較良好的鍵結，可以幫助穩定金屬進行催化反應。3a配位基應用在Suzuki-Miyaura 耦合反應上，對於芳香族溴化物，可得到良好的效率；芳香族氯化物則是對於低活性基質有良好的產率。而3d配位基則是可以應用在Heck反應中，對於芳香族溴化物可應用於各種不同的官能基當中。

A series of 1,2-diaminocyclohexane and o-phenylenediamine derivatives as diamine ligands (3a-3h) were prepared, and further reactions led to the formation of secondary phosphine oxides (SPOs, 4a-4c).The molecular structures of 4c and complexes 3a_Pd, 3b_Pd, 3c_Pd, 3d_Cu were determined by single crystal X-ray diffraction methods. After screening of the ligands, diamines showed better coordinating capacities toward the palladium salt. These ligands can stabilize the palladium complexes during the catalytic reactions. Catalysis of the Suzuki-Miyaura coupling reactions with 3a for the aryl bromides showed good yields, nevertheless, lower reactivities were observed for aryl chlorides. In addition, 3d was employed in the Heck reaction as ligand. It exhibited a good tolerance of functional groups for the aryl bromides.

第一章 序論 1
第一節 耦合反應概述 2
第二節 鈀催化Suzuki-Miyaura 耦合反應 4
第三節 鈀催化Heck 耦合反應 8
第四節 常見的配位基簡介 12
第五節 二級氧化膦基(Secondary Phosphine Oxide, SPO)之簡介 17
第六節 雙氮配位基簡介 21
第七節 研究方向 25
第二章 結果與討論 26
第一節 1,2-環己二胺、鄰苯二胺衍生物及SPOs的製備及鑑定 27
第二節 1,2-環己二胺與金屬形成之錯合物的合成及鑑定 34
第三節 配位基3和4應用於Suzuki 耦合反應催化芳香族溴化物 46
第四節 配位基3a應用於Suzuki耦合反應催化芳香族氯化物 56
第五節 配位基3應用於Heck 耦合反應催化芳香族溴化物 62
第三章 結論 69
第四章 實驗 70
第一節 儀器與藥品 71
第二節 操作技巧 76
第三節 合成與鑑定 77
第四節 Suzuki 及Heck 耦合反應步驟 91
第五章 參考文獻 100
附錄 104
光譜數據 105
晶體數據 134
耦合產物數據 182

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