Radical–anion coupling through reagent design: hydroxylation of aryl halides

Andrew J. Greener; Patrycja Ubysz; Will Owens-Ward; George Smith; Ivan Ocaña; Adrian C. Whitwood; Victor Chechik; Michael J. James

doi:10.1039/d1sc04748e

Radical–anion coupling through reagent design: hydroxylation of aryl halides

Andrew J. Greener, Patrycja Ubysz, Will Owens-Ward, George Smith, Ivan Ocaña, Adrian C. Whitwood, Victor Chechik, Michael J. James^*

^*Corresponding author for this work

Chemistry

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

Abstract

The design and development of an oxime-based hydroxylation reagent, which can chemoselectively convert aryl halides (X = F, Cl, Br, I) into phenols under operationally simple, transition-metal-free conditions is described. Key to the success of this approach was the identification of a reducing oxime anion which can interact and couple with open-shell aryl radicals. Experimental and computational studies support the proposed radical-nucleophilic substitution chain mechanism.

Original language	English
Pages (from-to)	14641-14646
Number of pages	6
Journal	Chemical Science
Volume	12
Issue number	43
DOIs	https://doi.org/10.1039/d1sc04748e
Publication status	Published - 22 Oct 2021

Bibliographical note

Funding Information:
The authors would like to thank the Wild Fund, the University of York, the Leverhulme Trust (for an Early Career Fellowship, ECF-2019-135, M. J. J.) and the Royal Society (Research Grant RGS\R1\201268) for nancial support. We would also like to thank Prof. Peter O'Brien and Dr William P. Unsworth for helpful discussions.

Publisher Copyright:
© The Royal Society of Chemistry 2021.

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abstract = "The design and development of an oxime-based hydroxylation reagent, which can chemoselectively convert aryl halides (X = F, Cl, Br, I) into phenols under operationally simple, transition-metal-free conditions is described. Key to the success of this approach was the identification of a reducing oxime anion which can interact and couple with open-shell aryl radicals. Experimental and computational studies support the proposed radical-nucleophilic substitution chain mechanism.",

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AU - Greener, Andrew J.

AU - Ubysz, Patrycja

AU - Owens-Ward, Will

AU - Smith, George

AU - Ocaña, Ivan

AU - Whitwood, Adrian C.

AU - Chechik, Victor

AU - James, Michael J.

N1 - Funding Information: The authors would like to thank the Wild Fund, the University of York, the Leverhulme Trust (for an Early Career Fellowship, ECF-2019-135, M. J. J.) and the Royal Society (Research Grant RGS\R1\201268) for nancial support. We would also like to thank Prof. Peter O'Brien and Dr William P. Unsworth for helpful discussions. Publisher Copyright: © The Royal Society of Chemistry 2021.

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AB - The design and development of an oxime-based hydroxylation reagent, which can chemoselectively convert aryl halides (X = F, Cl, Br, I) into phenols under operationally simple, transition-metal-free conditions is described. Key to the success of this approach was the identification of a reducing oxime anion which can interact and couple with open-shell aryl radicals. Experimental and computational studies support the proposed radical-nucleophilic substitution chain mechanism.

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Radical–anion coupling through reagent design: hydroxylation of aryl halides

Abstract

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