Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/96270
標題: Amido-substituent in Biphenyl as Directing Group in Palladium-Catalyzed Phosphination Reaction through C-H Bond Functionalization
以醯胺作為指向基團利用鈀金屬催化進行聯苯碳-氫鍵活化的磷酸化反應
作者: Ching-Yu Wang
王靖諭
關鍵字: 碳氫鍵活化
碳氫鍵官能化
指向基團
醯胺
二級氧化磷基

咔唑
C-H activation
C-Hfunctionalization
Directing group
Acetamide
Secondary phosphine oxide
Palladium
Carbazole.
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摘要: The synthesis of N-(2'-(diphenylphosphoryl)-[1,1'-biphenyl]-2-yl)-2,2,2-trifluoroacetamide (3a) has been achieved from the palladium catalytic and Ag(I)-assisted C-H functionalization of 2-trifluoroacetamidebipheny (1a) via phosphination. The source of diphenylphosphine oxide has to be added rather slowly by Syringe Pump (KDS100) to achieve the goal. The crystal structure of 3a was determined by X-ray crystal diffraction methods. Indeed, the phosphination took place at the ortho-position of interannular ring. A reaction mechanism is proposed based on the experimental results. While the substituent -CF3 in 1a is replaced by -C6H5, similar results were obtained and produced 3c. Nevertheless, a carbazole derivative 4b was obtained while the substituent is changed to an electron-withdrawing group, -CH3. It was found that the type of reaction product could be greatly affected by the substituent on the acetamidebiphenyl as well as by acidic or base reaction condition.
本研究使用聯苯三氟乙酰胺1a做為起始物,與對甲苯基膦氧化物反應,後者利用自動注射幫浦緩慢加入。在金屬鈀化合物的催化下進行反應,最後形成碳-磷鍵產物3a,並且鑑定了3a的晶體結構。推測反應是透過金屬鈀化合物先將聯苯三氟乙酰胺活化,使對甲苯基膦氧化物脫去氫後接到金屬鈀化合物,再進行碳-磷鍵耦合反應,最終產生碳-磷鍵產物。根據優選條件推出可行的反應機制。 這研究也嘗試使用不同的推拉電子能力的取代基,在相同的條件下進行反應,發現當反應物是聯苯乙酰胺上的取代基是具有推電子能力的甲基時,其產物為carbazole型態的衍生物4b;當取代基是具有拉電子能力的五氟苯時,主產物是具有碳-磷鍵產物3c,和形成3a的情形類似。 這些反應結果發現聯苯乙酰胺上的取代基的不同推拉電子基效應會影響反應機制。另外,不同酸鹼性條件也會影響反應結果。
URI: http://hdl.handle.net/11455/96270
文章公開時間: 2017-08-29
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