水溶性鐵觸媒催化One-pot Sonogashira-Hagihara反應

One-pot Iron(III) /Cationic 2,2’-Bipyridyl System Catalyzed Sonogashira-Hagihara Coupling in Water

洪慈婷(Tzu-Ting Hung)

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(2010年)

摘要

利用aryl halide 和terminal alkyne合成出Csp2-Csp cross-coupling的產物為有名的Sonogashira-Hagihara reaction。近年來，此人名反應被發展出許多過渡金屬都可作為催化劑，例如：Pd、Ni、Cu、Co等，而最近新興的重要金屬為鐵，鐵是過渡金屬中相對較無害、便宜和易取得，對環境傷害較小，搭配實驗室合成出的水溶性觸媒可以在水中有很好的產率，達到環保和綠色化學的概念。 以往Sonogashira-Hagihara反應需要加入一價銅當共催化劑，而在此系統中不需要加入銅，我們利用加入Zn幫助產物的生成，即可合成出Csp2-Csp cross-coupling的產物都有不錯的產率。
再者利用1-aryl-3-methyl-1-butyn-3-ol做為terminal alkynes的來源，達到one-pot反應效果，不需再多一個分離與純化的步驟，可以減少有機溶液的使用量，使反應更加環保。

關鍵字

鐵金屬 ； 水溶性觸媒 ； 綠色化學 ； Sonogashira反應 ； one-pot

並列摘要

The cross-coupling between an aryl halide and terminal alkyne catalyzed by palladium catalyst is widely known as the Sonogashira-Hagihara reaction. It provides a powerful method for the preparation of aryl alkynes which are important compounds for material sciences and medicinal chemistry.

In the past decade, an effort was made to develop efficient catalytic systems by using cheap transition metals, such as copper or nickel catalysts and with adequate ligands. Recently, the Sonogashira-Hagihara reaction was developed on iron-catalyed because iron is the cheapest transition metal, non-toxic, and environmentally benign. However, such reactions still use organic solvents as reaction medium.

Here we report a green process using FeCl3．6H2O as a catalyst in the cleanest solvent, water, for Sonogashira-Hagihara reaction. We introduced a water-soluble cationic 2,2´-bipyridyl ligand to bring the catalyst into aqueous phase enabled the reaction of aryl iodies with terminal alkynes and 1-aryl-3-methyl-1-butyn-3-ol to form diaryl alkynes in water under air in good to excellent yields.

Specially, terminal alkynes can be generated in situ from 1-aryl-3-methyl-1-butyn -3-ol. This procedure reduced the wastage of organic solvents for the isolation of terminal alkynes.

並列關鍵字

Iron ； water-soluble catalyst ； green chemistry ； Sonogashira-Hagihara reaction ； one-pot.

參考文獻

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