以鈀觸媒在水相催化Allyl Aryl Sulfones 進行分子間偶合形成 Aryl-(E)-3-Arylprop-2-enyl Sulfones

Pd-Catalyzed Intermolecular Coupling of Allyl Aryl Sulfones Leading to the formation of Aryl (E)-3-Arylprop-2-enyl Sulfones in Aqueous Phase

吳珮瑜(Pei-Yu Wu)

指導教授 ： 蔡福裕

國立臺北科技大學/工程學院/有機高分子研究所/碩士(2013年)

摘要

我們利用實驗室自行開發之雙陽離子水溶性配位基，和不同金屬形成錯合物在水相中進行數種碳-碳鍵生成反應，已逐漸發展出具高催化效果的觸媒。因此，本論文利用PdCl2(NH3)2 與陽離子2,2’-bipyridyl ligand 配位形成水相催化系統，於芳香性苯硼酸與HBF4 酸性條件下催化allyl aryl sulfones 進行分子間偶合反應形成
Aryl-(E)-3-arylprop-2-enyl sulfones。當在空氣下約得到20%左右芳香性苯硼酸與allyl aryl sulfone 進行之 oxidative Heck-type coupling 的副產物。若反應條件控制在氮氣下可抑制副產物的形成，並獲得高產率的allyl aryl sulfone 分子間偶合的產物。此外，我們使用地球含量最多、對環境汙染最少、最環保的溶劑，水做為此
反應的主要溶劑，使此反應符合綠色化學的規範。

關鍵字

鈀 ； 離子性2,2’雙吡啶 ； 分子間偶合 ； 水 ； 綠色化學

並列摘要

We have recently prepared a water-soluble cationic 2,2’-bipyridyl ligand and utilized it to bring many type of transition-metals into the aqueous phase for car-bon-carbon bond forming reactions. As part of our continuing efforts in the devel-opment of green catalytic systems, we report herein the combination of Pd(NH3)2Cl2 and cationic 2,2’-bipyridyl ligand was found to be an efficient catalyst for the inter-molecular coupling of allyl aryl sulfones in the presence of arylboronic acids and HBF4 in water, which led to the formation of aryl (E)-3-arylprop-2-enyl sulfones. When the reaction was conducted under air, about 20% oxidative Heck-type coupling by-product, produced from the coupling of aryl boronic acid and allyl aryl sulfone, was obtained. Therefore, reaction was performed under N2 atmosphere to suppress the formation of by-product and give the desired intermolecular coupling product in good to high yields.
In addition, we use the Earth's most abundant, least polluting, and the most environmentally-friendly solvent, water, as the reaction medium to meet the goal of green
chemistry.

並列關鍵字

palladium ； cationic 2,2’-bipyridyl ； intermolecular coupling ； water ； green chemistry

參考文獻

[1] T. Mizoroki, K. Mori, A. Ozaki, Bull. Chem. Soc. Jpn. 1971, 44, 581.

[2] R. F. Heck, J. P. Nolley, Jr., J. Am. Chem. 1972, 37, 2320.

[3] K. C. Nicolaou, P. G. Bulger, D. Sarlah, Angew. Chem. Int. Ed. 2005, 44, 4442.

[5] H. A. Dieck, F. R. Heck, J. Organomet. Chem. 1975, 93, 259.

[6] K. Sonogashira, Y. Tohda, N. Hagihara, Tetrahedron Lett. 1975, 93, 259.