From Ketones to Esters by a Cu-Catalyzed Highly Selective C(CO)鈥揅(alkyl) Bond Cleavage: Aerobic Oxidation and Oxygenation with Air

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• 作者：Xiaoqiang Huang ; Xinyao Li ; Miancheng Zou ; Song Song ; Conghui Tang ; Yizhi Yuan ; Ning Jiao
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：October 22, 2014
• 年：2014
• 卷：136
• 期：42
• 页码：14858-14865
• 全文大小：595K
• ISSN：1520-5126

文摘

The Cu-catalyzed aerobic oxidative esterification of simple ketones via C鈥揅 bond cleavage has been developed. Varieties of common ketones, even inactive aryl long-chain alkyl ketones, are selectively converted into esters. The reaction tolerates a wide range of alcohols, including primary and secondary alcohols, chiral alcohols with retention of the configuration, electron-deficient phenols, as well as various natural alcohols. The usage of inexpensive copper catalyst, broad substrate scope, and neutral and open air conditions make this protocol very practical. ¹⁸O labeling experiments reveal that oxygenation occurs during this transformation. Preliminary mechanism studies indicate that two novel pathways are mainly involved in this process.