The Origin of Catalytic Benzylic C−H Oxidation over a Redox‐Active Metal–Organic Framework. (4th June 2021)

• Record Type: Journal Article
• Authors: 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
• Is Part Of: Angewandte Chemie. Volume 133:Number 28(2021)
• Page Start: 15371
• Page End: 15375
• Publication Date: 2021-06-04
• Subjects: benzylic oxidation -- catalysis -- copper -- electron paramagnetic resonance -- metal–organic framework; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202102313
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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 [Cu2 II (O2 CR)4 ] 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 t BuOOH (tert‐butyl hydroperoxide) via partial reduction to [Cu II Cu I (O2 CR)4 ] species. Abstract : The oxidation of benzylic C−H groups in a broad range of substrates under mild conditions has been achieved using a robust metal–organic framework, MFM‐170, incorporating redox‐active [Cu2 II (O2 CR)4 ] paddlewheel nodes. EPR spectroscopy and synchrotron X‐ray diffraction have identified the critical role of the paddlewheel moiety in activating the oxidant t BuOOH ( tert ‐butyl hydroperoxide) via partial reduction to [Cu II Cu I (O2 CR)4 ] species.