The origin of catalytic benzylic C‐H oxidation over a redox‐active metal‐organic framework

Louis Kimberley; Alena M. Sheveleva; Jiangnan Li; Joseph H. Carter; Xinchen Kang; Gemma L. Smith; Xue Han; Sarah J. Day; Chiu C. Tang; Floriana Tuna; Eric J. L. Mcinnes; Sihai Yang; Martin Schröder

doi:10.1002/anie.202102313

The origin of catalytic benzylic C‐H oxidation over a redox‐active metal‐organic framework

Louis Kimberley, Alena M. Sheveleva, Jiangnan Li, Joseph H. Carter, Xinchen Kang, Gemma L. Smith, Xue Han, Sarah J. Day, Chiu C. Tang, Floriana Tuna, Eric J. L. Mcinnes, Sihai Yang, Martin Schröder

Diamond Light Source Ltd

Research output: Contribution to journal › Article › peer-review

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 metals catalysts. Here, 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 [Cu2II(O2CR)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 tBuOOH (t‐butyl hydroperoxide) via partial reduction to [CuIICuI(O2CR)4] species.

Original language	English
Pages (from-to)	15243-15247
Journal	Angewandte Chemie International Edition
Volume	60
Issue number	28
DOIs	https://doi.org/10.1002/anie.202102313
Publication status	Published - 13 Apr 2021

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https://onlinelibrary.wiley.com/doi/10.1002/anie.202102313

EPSRC National Research Facility for Electron Paramagnetic Resonance
Collison, D. (Academic lead), Mcinnes, E. (Academic lead), Tuna, F. (Academic lead), Bowen, A. (Academic lead), Shanmugam, M. (Senior Technical Specialist), Brookfield, A. (Technical Specialist), Fleming, E. (Other) & Cliff, M. (Platform Lead)
FSE Research
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Kimberley, L., Sheveleva, A. M., Li, J., Carter, J. H., Kang, X., Smith, G. L., Han, X., Day, S. J., Tang, C. C., Tuna, F., Mcinnes, E. J. L., Yang, S., & Schröder, M. (2021). The origin of catalytic benzylic C‐H oxidation over a redox‐active metal‐organic framework. Angewandte Chemie International Edition, 60(28), 15243-15247. https://doi.org/10.1002/anie.202102313

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title = "The origin of catalytic benzylic C‐H oxidation over a redox‐active metal‐organic framework",

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 metals catalysts. Here, 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 [Cu2II(O2CR)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 tBuOOH (t‐butyl hydroperoxide) via partial reduction to [CuIICuI(O2CR)4] species.",

author = "Louis Kimberley and Sheveleva, {Alena M.} and Jiangnan Li and Carter, {Joseph H.} and Xinchen Kang and Smith, {Gemma L.} and Xue Han and Day, {Sarah J.} and Tang, {Chiu C.} and Floriana Tuna and Mcinnes, {Eric J. L.} and Sihai Yang and Martin Schr{\"o}der",

year = "2021",

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doi = "10.1002/anie.202102313",

language = "English",

volume = "60",

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T1 - The origin of catalytic benzylic C‐H oxidation over a redox‐active metal‐organic framework

AU - Kimberley, Louis

AU - Sheveleva, Alena M.

AU - Li, Jiangnan

AU - Carter, Joseph H.

AU - Kang, Xinchen

AU - Smith, Gemma L.

AU - Han, Xue

AU - Day, Sarah J.

AU - Tang, Chiu C.

AU - Tuna, Floriana

AU - Mcinnes, Eric J. L.

AU - Yang, Sihai

AU - Schröder, Martin

PY - 2021/4/13

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N2 - 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 metals catalysts. Here, 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 [Cu2II(O2CR)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 tBuOOH (t‐butyl hydroperoxide) via partial reduction to [CuIICuI(O2CR)4] species.

AB - 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 metals catalysts. Here, 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 [Cu2II(O2CR)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 tBuOOH (t‐butyl hydroperoxide) via partial reduction to [CuIICuI(O2CR)4] species.

U2 - 10.1002/anie.202102313

DO - 10.1002/anie.202102313

M3 - Article

SN - 1433-7851

VL - 60

SP - 15243

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JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 28

ER -

The origin of catalytic benzylic C‐H oxidation over a redox‐active metal‐organic framework

Abstract

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EPSRC National Research Facility for Electron Paramagnetic Resonance

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