The Gold-Catalyzed Hydroarylation of Alkynes with Electron-Rich Heteroarenes - A Kinetic Investigation and New Synthetic Possibilities

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• 作者：Jasmin Schieß ; l ; Matthias Rudolph and A. Stephen K. Hashmi
• 刊名：Advanced Synthesis & Catalysis
• 出版年：2017
• 出版时间：February 20, 2017
• 年：2017
• 卷：359
• 期：4
• 页码：639-653
• 全文大小：2635K
• ISSN：1615-4169

文摘

The gold-catalyzed mono-hydroarylation and two-fold hydroarylation of alkynes with electron-rich heteroarenes was analyzed by a ¹H NMR kinetic study. The obtained rate constants for the decreasing alkyne concentration provide information on the reactivity of this addition reaction. The examinations show the orthogonal reactivity of gold and a proton for the two reaction steps. The first hydroarylation is exclusively promoted by gold(I), whereas the second step is premised on a proton which will be reversibly derived from the formation of σ,π-acetylide complexes from the terminal alkynes or by interaction with solvents. Based on kinetic data, it was possible to synthesize a large range of mono-adducts in moderate to good yields, furthermore the synthesis of hetero-di-adducts, bearing two different substituents, was explored.