Uncovering the Mechanism of the Ag(I)/Persulfate-Catalyzed Cross-Coupling Reaction of Arylboronic Acids and Heteroarenes

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• 作者：Niki R. Patel ; Robert A. Flowers ; II
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：March 27, 2013
• 年：2013
• 卷：135
• 期：12
• 页码：4672-4675
• 全文大小：254K
• 年卷期：v.135,no.12(March 27, 2013)
• ISSN：1520-5126

文摘

The catalytic cross-coupling of arylboronic acids with pyridines through single-electron oxidation provides efficient access to substituted heterocycles. Despite the importance of this reaction, very little is known about its mechanism, and as a consequence, it is unclear whether the full scope of the transformation has been realized. Here we present kinetic and spectroscopic evidence showing a high degree of complexity in the reaction system. The mechanism derived from these studies shows the activation of Ag(I) for reduction of persulfate and an off-cycle protodeboronation by the pyridine substrate. These results provide key mechanistic insights that enable control of the off-cycle process, thus providing higher efficiency and yield.