Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/90604
標題: 一、Preparation of Secondary Phosphine Oxides via Nucleophilic Attack on Imines and Application in Palladium-Catalyzed Cross-coupling Reactions 二、Study on the P-N Bond Hydrolysis of Diaminophosphine Oxide Pre-ligands
一、製備經由在亞胺上進行親核性攻擊反應之二級氧化膦基與其鈀金屬錯合物應用於耦合反應之研究 二、二胺基膦氧化物中磷-氮鍵水解的反應機制研究
作者: 胡棧喻
Chan-Yu Hu
關鍵字: Secondary Phosphine Oxide;Suzuki-Miyaura coupling reaction;P-N bond hydrolysis;二級氧化膦基;Suzuki-Miyaura 耦合反應;磷-氮鍵水解
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摘要: 
In the first part of this work, several N-aryl secondary amine type of secondary phosphine oxides (SPOs, 3a-3g) containing C─P bond had been successfully prepared. The molecular structures of 3b、3e、3g and complexes 4e were determined by single crystal X-ray diffraction methods. After screening ligands 3a-3g for Suzuki-Miyaura cross-coupling reaction, ligand 3b exhibited satisfactory efficiencies.
Unexpectedly, four palladium complexes were obtained from the reaction H_3c with Pd(COD)Cl2. Pd1_H_3c has a cis form structure. Pd2'_H_3c and Pd2'_H_3c were obtained from the water-assisted C-N bond cleavage, while Pd3_H_3c was yielded via P-N bond hydrolysis. It is worthy of noting that this methodology for making C-P bond and N-P bond containing SPOs is unprecedented.
In the second part of this work, two known compounds Heteroatom-substituted secondary phosphine oxides(HASPO)
H_1a & H_1b were synthesized and studied for their stabilities toward hydrohysis. It was found that H_1b is much more thermodynamically stable toward water than H_1a in neutral solution.

本研究第一部分製備出以芳香環二級胺為架構的含碳─磷鍵之二級氧化膦基3a-3g。並成功利用X-ray單晶繞射法鑑定分子3b、3e、及3g和錯合物4e等結構。經過優選後,發現配位基3b應用在Suzuki-Miyaura耦合反應上,對於芳香族溴化物有不錯的表現。
此外,也順利地將H_3c和Pd(COD)Cl2反應,形成四種特殊的鍵結模式。其中Pd1_H_3c為cis form,而Pd2'_H_3c及Pd2'_H_3c因水存在下形成C─N鍵斷裂的錯合物。Pd3_H_3c則是P─N鍵斷裂下形成的晶體。另外值得一提的是,這種使用第三丁基鋰以及1-甲基咪唑鋰做為親和性試劑來合成二級氧化膦基的方法在其他文獻上尚未被報導過。
本研究第二部分重新製備HASPO (Heteroatom-substituted secondary phosphine oxides) H_1a和H_1b並以NMR技術量測其水解過程。發現H_1b比H_1a在水解上比較穩定。
本研究第二部分重新製備HASPO (Heteroatom-substituted secondary phosphine oxides) H_1a和H_1b並以NMR技術量測其水解過程。發現H_1b比H_1a在水解上比較穩定。
URI: http://hdl.handle.net/11455/90604
Rights: 同意授權瀏覽/列印電子全文服務,2017-07-16起公開。
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