親核性試劑和鈀金屬催化烯雙炔化合物之環化反應

Synthesis of Heteorcycles and Aromatic Compounds via Nucleophilic-Promoted and Palladium-Catalyzed Cycloaromatization of Enediynes

李佳螢(Chia-Ying Lee)

指導教授 ： 吳明忠

高雄醫學大學/藥學院/藥學研究所/博士(2006年)

摘要

在過去的幾年中，我們實驗室曾對烯雙炔類的化合物進行陰離子芳香性環化反應來得到異喹啉酮、啡啶酮和聯苯之產物。在本論文中我們將繼續對烯雙炔化合物的環化模式進行的研究與探討，首先介紹二苯并呋喃和咔唑的合成方法研究。合成二苯并呋喃是藉由2-(6-substituted 3(Z)-hexen-1,5-diynyl)phenyl tert-butyldimethyl ethers與甲醇鈉再迴流甲醇溶液下進行反應而得，此反應有不錯的產率。另ㄧ方面是咔唑的合成研究，我們發現到最佳的反應條件是利用N-Acetyl-(Z)-2-(6-substituted 3(Z)-hexen-1,5-diynyl)anilines與KOtBu在NMP當溶媒溫度攝氏80度下反應得到高產率之咔唑。
另一個有趣的發現是利用N-acetyl-2-(6-substituted 3(Z)-hexen-1,5-diynyl)anilines或N-benzoyl-2-(6-substituted 3(Z)-hexen-1,5-diynyl)anilines與催化量之鈀金屬的催化劑反應來得到具多取代的萘環化合物。最後我們發現1,2-bis(substituted ethynyl)benzenes與5 mole% PdCl2和兩當量CuCl2反應可得到不錯產率的benzofulvenes和少量之indenones。

關鍵字

二苯并呋喃 ； 咔唑 ； 陰離子芳香性環化反應 ； 烯雙炔 ； 過渡金屬催化

並列摘要

Recently, synthesis of several aromatic compounds, including isoquinolones, phenanthridinones, and biphenyls have been achieved by anionic cycloaromatization of enediynes in our lab. As part of our on going researches, these applications were applied to the preparation of two series of bioactive compounds, dibenzofurans and carbazoles, from various enediyne precursors. First of all, reaction of 2-(6-substituted 3(Z)-hexen-1,5-diynyl)phenyl tert-butyldimethyl ethers with sodium methoxide at reflux in methanol gave dibenzofurans in good yields. On the other hand, the synthesis of carbazoles were achieved by the reaction of N-acetyl-2-(6-substituted 3(Z)-hexen-1,5-diynyl)anilines with KOtBu in NMP at 80 oC.
Interestingly, when N-acetyl-2-(6-substituted 3(Z)-hexen-1,5-diyny
l)anilines or N-benzolyl-2-(6-substituted 3(Z)-hexen-1,5-diynyl)anilines were treated with catalytic amount of palladium, the reactions gave naphthalene derivatives in 22-48 % yields. Finally, treatment of 1,2-bis(substituted ethynyl)benzenes with 5 mole% of PdCl2 and two equivalents of CuCl2 in acetonitrile at 60 oC gave the benzofulvene adducts in good yields along with small amount of indenones.

並列關鍵字

anionic cycloaromatization ； enediyne ； dibenzofurans ； carbazoles ； naphthalene ； benzofulvene ； indenones

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