Graduate School of Pharmaceutical Sciences, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Advanced Elements Chemistry Research Team, RIKEN Center for Sustainable Resource Science, and Elements Chemistry Laboratory, RIKEN , 2-1 Hirosawa, Wako-shi, Saitama 351-0198, Japan.
J Am Chem Soc. 2016 Jul 27;138(29):9166-71. doi: 10.1021/jacs.6b03855. Epub 2016 Jul 14.
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.
脱质子导向的芳基/杂芳基 C-H 键邻位铜化反应，随后用叔丁基过氧氢（t-BuOOH）氧化，以高产率、高区域和化学选择性得到了官能化的酚类化合物。DFT 计算表明，该羟化反应通过铜（I → III → I）氧化还原机制进行。该反应在使用 BnONH2 的芳基 C-H 氨化中的应用有效地得到了相应的伯苯胺。这些反应具有广泛的适用范围和良好的官能团兼容性。这些转化的催化版本也得到了证明。
