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

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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
Journal	Angewandte Chemie International Edition
DOIs	https://doi.org/10.1002/anie.202102313
Publication status	Published - 13 Apr 2021

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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",

month = apr,

day = "13",

doi = "10.1002/anie.202102313",

language = "English",

journal = "Angewandte Chemie International Edition",

issn = "1433-7851",

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TY - JOUR

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

Y1 - 2021/4/13

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

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

ER -

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

Abstract

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