Direct Hydroxylation and Amination of Arenes via Deprotonative Cupration

作者：Tezuka Noriyuki; Shirnojo Kohei; Hirano Keiichi^*; Komagawa Shinsuke; Yoshida Kengo; Wang Chao; Miyamoto Kazunori; Saito Tatsuo; Takita Ryo; Uchiyama Masanobu^*

来源：Journal of the American Chemical Society, 2016, 138(29): 9166-9171.

DOI：10.1021/jacs.6b03855

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.

• 出版日期2016-7-27
• 单位RIKEN