Au(I)-Catalyzed Cycloisomerizations Terminated by sp3 C−H Bond Insertion

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• 作者：Yoshikazu Horino*^† ; ; Takuya Yamamoto^† ; ; Kohki Ueda^† ; ; Shigeyasu Kuroda^† ; ; F. Dean Toste*^‡ ;
• 刊名：Journal of the American Chemical Society
• 出版年：2009
• 出版时间：March 4, 2009
• 年：2009
• 卷：131
• 期：8
• 页码：2809-2811
• 全文大小：173K
• 年卷期：v.131,no.8(March 4, 2009)
• ISSN：1520-5126

文摘

The gold(I)-catalyzed cycloisomerization of 1,5-enynes and 1,4-allylallenes to tetracyclododecane and tetracyclotridecane derivatives, respectively, is reported. Complexation of the cationic gold(I) complex to either the alkyne or allene moiety induces an intramolecular addition of the alkene, leading to a gold(I)-stabilized carbenoid intermediate. This intermediate undergoes a formal sp³ C−H insertion to generate the tetracyclic adduct. A series of deuterium labeling experiments showed that the C−H functionalization step proceeds with an inverse kinetic isotope effect.