Divergence between Organometallic and Single-Electron-Transfer Mechanisms in Copper(II)-Mediated Aerobic C鈥揌 Oxidation

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• 作者：Alison M. Suess ; Mehmed Z. Ertem ; Christopher J. Cramer ; Shannon S. Stahl
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：July 3, 2013
• 年：2013
• 卷：135
• 期：26
• 页码：9797-9804
• 全文大小：521K
• 年卷期：v.135,no.26(July 3, 2013)
• ISSN：1520-5126

文摘

Copper(II)-mediated C鈥揌 oxidation is the subject of extensive interest in synthetic chemistry, but the mechanisms of many of these reactions are poorly understood. Here, we observe different products from Cu^II-mediated oxidation of N-(8-quinolinyl)benzamide, depending on the reaction conditions. Under basic conditions, the benzamide group undergoes directed C鈥揌 methoxylation or chlorination. Under acidic conditions, the quinoline group undergoes nondirected chlorination. Experimental and computational mechanistic studies implicate an organometallic C鈥揌 activation/functionalization mechanism under the former conditions and a single-electron-transfer mechanism under the latter conditions. This rare observation of divergent, condition-dependent mechanisms for oxidation of a single substrate provides a valuable foundation for understanding Cu^II-mediated C鈥揌 oxidation reactions.