Selective electrochemical generation of benzylic radicals enabled by ferrocene-based electron-transfer mediators

Alastair J.J. Lennox; Jordan E. Nutting; Shannon S. Stahl

doi:10.1039/c7sc04032f

Selective electrochemical generation of benzylic radicals enabled by ferrocene-based electron-transfer mediators

Alastair J.J. Lennox, Jordan E. Nutting, Shannon S. Stahl

School of Chemistry

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Abstract

The generation and intermolecular functionalisation of carbon-centred radicals has broad potential synthetic utility. Herein, we show that benzylic radicals may be generated electrochemically from benzylboronate derivatives at low electrode potentials (ca. -0.3 V vs. Cp₂Fe^0/+) via single electron oxidation. Use of a catalytic quantity of a ferrocene-based electron-transfer mediator is crucial to achieve successful radical functionalisation and avoid undesirable side reactions arising from direct electrochemical oxidation or from the use of stoichiometric ferrocenium-based oxidants.

Original language	English
Pages (from-to)	356-361
Number of pages	6
Journal	Chemical Science
Volume	9
Issue number	2
Early online date	6 Nov 2017
DOIs	https://doi.org/10.1039/c7sc04032f
Publication status	Published - 1 Jan 2018

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Dr Alastair J J Lennox
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- School of Chemistry - Royal Society University Research Fellow and Proleptic Associate Professor
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title = "Selective electrochemical generation of benzylic radicals enabled by ferrocene-based electron-transfer mediators",

abstract = "The generation and intermolecular functionalisation of carbon-centred radicals has broad potential synthetic utility. Herein, we show that benzylic radicals may be generated electrochemically from benzylboronate derivatives at low electrode potentials (ca. -0.3 V vs. Cp2Fe0/+) via single electron oxidation. Use of a catalytic quantity of a ferrocene-based electron-transfer mediator is crucial to achieve successful radical functionalisation and avoid undesirable side reactions arising from direct electrochemical oxidation or from the use of stoichiometric ferrocenium-based oxidants.",

author = "Lennox, {Alastair J.J.} and Nutting, {Jordan E.} and Stahl, {Shannon S.}",

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T1 - Selective electrochemical generation of benzylic radicals enabled by ferrocene-based electron-transfer mediators

AU - Lennox, Alastair J.J.

AU - Nutting, Jordan E.

AU - Stahl, Shannon S.

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Y1 - 2018/1/1

N2 - The generation and intermolecular functionalisation of carbon-centred radicals has broad potential synthetic utility. Herein, we show that benzylic radicals may be generated electrochemically from benzylboronate derivatives at low electrode potentials (ca. -0.3 V vs. Cp2Fe0/+) via single electron oxidation. Use of a catalytic quantity of a ferrocene-based electron-transfer mediator is crucial to achieve successful radical functionalisation and avoid undesirable side reactions arising from direct electrochemical oxidation or from the use of stoichiometric ferrocenium-based oxidants.

AB - The generation and intermolecular functionalisation of carbon-centred radicals has broad potential synthetic utility. Herein, we show that benzylic radicals may be generated electrochemically from benzylboronate derivatives at low electrode potentials (ca. -0.3 V vs. Cp2Fe0/+) via single electron oxidation. Use of a catalytic quantity of a ferrocene-based electron-transfer mediator is crucial to achieve successful radical functionalisation and avoid undesirable side reactions arising from direct electrochemical oxidation or from the use of stoichiometric ferrocenium-based oxidants.

U2 - 10.1039/c7sc04032f

DO - 10.1039/c7sc04032f

M3 - Article (Academic Journal)

C2 - 29732109

AN - SCOPUS:85040198571

SN - 2041-6520

VL - 9

SP - 356

EP - 361

JO - Chemical Science

JF - Chemical Science

IS - 2

ER -

Selective electrochemical generation of benzylic radicals enabled by ferrocene-based electron-transfer mediators

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