近幾年隨著化學的發展，有機金屬催化有機合成反應日趨重要。以往必須以較多且較 困難的步驟所建構的分子，如今只需要以簡單的有機金屬催化反應即達成。因此有機 金屬錯合物催化有機合成反應的研究幾年來成為有機與無機化學研究的重點，不但吸 引相當多的化學家投入，也嚴然成為非常熱門與龐大的領域。此計劃內容便是以研究 銅金屬錯合物催化異原子偶合反應來探索更多建構有機化合物合成的新方法，以下分 為兩個主題介紹: (1) 銅金屬錯合物催化碳氧鍵及碳氮鍵偶合反應與其有機合成之應用: 傳統的銅金屬催化偶合反應(Ullmann coupling)能夠有效地催化碳-氧鍵與碳-氮 鍵的生成，然而其劇烈的反應條件卻使得此反應所能建構的化合物被大大的受到侷 限。因此許多配位基與條件的修飾不斷地在近年來被報導出來而使得此反應的應用範 圍越來越廣。我們期望能在傳統的理論基礎上加入條件的修飾而提高應用層面，並以 此修飾之催化方法來合成山酮素(Xanthone)等天然物之骨架。 (2) 銅金屬錯合物催化合環反應以建立天然物骨架或天然物結構: 銅金屬催化的偶合反應在近年來廣泛地被報導，其組合反應(domino reaction)能 有效應用於許多特殊結構的合成方面。因此我們打算研究新型組合反應的方法學，並 將其應用於建構天然物骨架如oxindole 以及pyrolidine 等結構，或是直接合成相關 天然物。此外，我們亦可將所研究發展之新型態銅催化組合反應應用於許多以傳統有 機方法較難合成之化合物，諸如phenanthridine 以及phenanthridinone 等結構。 In recent years, the transition metal catalytic reaction has attracted considerable attention, the importance of this field become higher and higher. In this proposal, we will describe the research plan in our group for the coming two0 years which involves the novel organometallic catalytic reaction, establishing the skeleton of natural products and new type of chelating ligands forming complexes with copper. A variety of new reactions catalyzed by copper complexes and application for some of these reactions are proposed. The important reactions that will be investigated are divided into two parts and summarized below. (1) Copper Catalyzed C-O and C-N bond Cross-Coupling Reaction as well as the Application in Organic Synthesis: Copper catalyzed Ullmann reaction involving the C-O or C-N cross-coupling reactions are convenient methods with properties of air stable and large scale formation. However, they were always performed with high catalyst loading or requirement of high temperatures which inhibited their application for the construction of complex molecules. The most effective modification for this Ullmann-type O-arylation is generally on the screening a suitable ligand. In this proposal we wish to find an effective combination of copper source with ligand to perform a general C-O and C-N cross-coupling, thus increase the possibility of the application to industrial consideration. (2) Copper Catalyzed Domino Reactions to Establish Natural Products or Their Skeleton: Oxindole and phenanthridinone are very important structures and commonly observed in natural products and material science. In this work, we will construct the above two structures via the copper catalyzed cyclization of substituted haloarenes with nitriles, which involves the base-promoted CN triple bond insertion tandem with the C-N cross-coupling reaction to afford our desired products. It also reveals great potential to apply this methodology on the construction of various heterocyclic compounds by the different combinations of the base-promoted nitrile insertion to other associated reactions.