利用水溶性銠觸媒進行苯乙炔類之聚合與[2+2+2]環化加成反應

使用過渡金屬作為催化劑進行有機物的合成已是現代化學最便利的方式之一，而在過渡金屬催化的有機反應中，多數使用有機溶劑及在惰性氣體下才能進行反應。然而，有機溶劑通常都具有毒性且易燃，也容易造成產物的分離不易。因此，以綠色化學的觀點，我們希望能利用水溶性的催化劑在水裡進行有機反應。如果可以利用水來取代有機溶劑有幾項優點，例如 :產物分離容易、不易燃燒、無毒且更可以保護人的健康與居住環境。本論文利用我們實驗室開發的水溶性配位基與銠金屬合成水溶性銠觸媒。首先，利用此催化劑，我們成功的在水中進行苯乙炔之聚合，且得到接近100% 順式的聚合物，更可以將觸媒回收再次進行聚合反應。水溶性銠觸媒仍可以有效的在水中進行苯乙炔類之聚合，同樣可以獲得順式以及高分子量的聚合物。此外，利用此水溶性銠觸媒催化不同的二炔及炔類在水中進行[2+2+2]環化加成反應，可獲得30%至90%的環化產物。

關鍵字

水溶性觸媒；銠；聚合反應； [2+2+2]環化加成

並列摘要

The use of transition metal as a catalyst is one of the most convenient methods in organic synthesis in modern chemistry. Most of the transition-metal-catalyzed reactions were carried out in organic solvents and under inert atmosphere. However, organic solvent are usually toxic, flammable and difficult to separate from reaction mixture. For this reaction, utilizing water-soluble catalyst to process the organic reaction in water is desired from the viewpoint of green chemistry. There are several advantages when water replaces of the organic solvent as a reaction medium, such as easy product isolation, nonflammable, nontoxic, and protection of public health and the living environment. In this report, we utilize cationic bipyridyl ligand which is synthesized by our group and coordinated to [Rh(cod)Cl]2 as a water soluble catalyst. At first, this water-soluble catalyst was successfully used to prepare stereoregular polyphenylacetylenes with a cis-content of near 100%. After filtration, the residual solution showed activity for the next polymerization. The Rhodium aqueous catalyst could polymerize several phenylacetylenes efficiently, giving high cis-content and high molecular weights of polymers. On the other hand, by utilizing this cationic catalytic system the [2+2+2] cycloaddition reaction for the formation of benzene derivatives in water under aerobic conditions for various diyne and alkyne was achieved affording the products in 30-90% yields.

並列關鍵字

water-soluble catalyst ； Rhodium ； polymerization ； [2+2+2] cycloatddition reaction

參考文獻

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利用水溶性銠觸媒進行苯乙炔類之聚合與[2+2+2]環化加成反應

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