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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. Cp 2Fe 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.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); National Inst. of Health (NIH) (United States)
OSTI Identifier:
1415512
Alternate Identifier(s):
OSTI ID: 1471035
Grant/Contract Number:  
FG02-05ER15690; DGE-1747503; CHE-1048642; 1S10 OD020022-1
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 9; Journal Issue: 2; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lennox, Alastair J. J., Nutting, Jordan E., and Stahl, Shannon S. Selective electrochemical generation of benzylic radicals enabled by ferrocene-based electron-transfer mediators. United States: N. p., 2017. Web. doi:10.1039/C7SC04032F.
Lennox, Alastair J. J., Nutting, Jordan E., & Stahl, Shannon S. Selective electrochemical generation of benzylic radicals enabled by ferrocene-based electron-transfer mediators. United States. doi:10.1039/C7SC04032F.
Lennox, Alastair J. J., Nutting, Jordan E., and Stahl, Shannon S. Mon . "Selective electrochemical generation of benzylic radicals enabled by ferrocene-based electron-transfer mediators". United States. doi:10.1039/C7SC04032F.
@article{osti_1415512,
title = {Selective electrochemical generation of benzylic radicals enabled by ferrocene-based electron-transfer mediators},
author = {Lennox, Alastair J. J. and Nutting, Jordan E. and Stahl, Shannon S.},
abstractNote = {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.},
doi = {10.1039/C7SC04032F},
journal = {Chemical Science},
number = 2,
volume = 9,
place = {United States},
year = {2017},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C7SC04032F

Citation Metrics:
Cited by: 5 works
Citation information provided by
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Works referenced in this record:

Molecular Catalysis of Electrochemical Reactions. Mechanistic Aspects
journal, July 2008

  • Sav√©ant, Jean-Michel
  • Chemical Reviews, Vol. 108, Issue 7, p. 2348-2378
  • DOI: 10.1021/cr068079z