Kimberley Louis, Sheveleva Alena M, Li Jiangnan, Carter Joseph H, Kang Xinchen, Smith Gemma L, Han Xue, Day Sarah J, Tang Chiu C, Tuna Floriana, McInnes Eric J L, Yang Sihai, Schröder Martin
Department of Chemistry, University of Manchester, Manchester, M13 9PL, UK.
Diamond Light Source, Harwell Science Campus, Oxfordshire, OX11 0DE, UK.
Angew Chem Int Ed Engl. 2021 Jul 5;60(28):15243-15247. doi: 10.1002/anie.202102313. Epub 2021 Jun 4.
Selective oxidation of benzylic C-H compounds to ketones is important for the production of a wide range of fine chemicals, and is often achieved using toxic or precious metal catalysts. Herein, we report the efficient oxidation of benzylic C-H groups in a broad range of substrates under mild conditions over a robust metal-organic framework material, MFM-170, incorporating redox-active [Cu (O CR) ] paddlewheel nodes. A comprehensive investigation employing electron paramagnetic resonance (EPR) spectroscopy and synchrotron X-ray diffraction has identified the critical role of the paddlewheel moiety in activating the oxidant BuOOH (tert-butyl hydroperoxide) via partial reduction to [Cu Cu (O CR) ] species.
将苄基C-H化合物选择性氧化为酮对于多种精细化学品的生产至关重要，并且通常使用有毒或贵金属催化剂来实现。在此，我们报道了在温和条件下，通过一种坚固的金属有机框架材料MFM-170，对多种底物中的苄基C-H基团进行高效氧化，该材料包含具有氧化还原活性的[Cu₂(μ-O₂CR)₂]桨轮节点。采用电子顺磁共振（EPR）光谱和同步加速器X射线衍射进行的全面研究已经确定了桨轮部分通过部分还原为[Cu₂(μ-O₂CR)₂]物种来激活氧化剂叔丁基过氧化氢（BuOOH）的关键作用。
Zotero 插件