Direct Hydroxylation and Amination of Arenes via Deprotonative Cupration

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• 作者：Noriyuki Tezuka ; Kohei Shimojo ; Keiichi Hirano ; Shinsuke Komagawa ; Kengo Yoshida ; Chao Wang ; Kazunori Miyamoto ; Tatsuo Saito ; Ryo Takita ; Masanobu Uchiyama
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：July 27, 2016
• 年：2016
• 卷：138
• 期：29
• 页码：9166-9171
• 全文大小：395K
• 年卷期：0
• ISSN：1520-5126

文摘

Deprotonative directed ortho cupration of aromatic/heteroaromatic C–H bond and subsequent oxidation with t-BuOOH furnished functionalized phenols in high yields with high regio- and chemoselectivity. DFT calculations revealed that this hydroxylation reaction proceeds via a copper (I → III → I) redox mechanism. Application of this reaction to aromatic C–H amination using BnONH₂ efficiently afforded the corresponding primary anilines. These reactions show broad scope and good functional group compatibility. Catalytic versions of these transformations are also demonstrated.