Williams, PJH, Boustead, GA, Heard, DE orcid.org/0000-0002-0357-6238 et al. (3 more authors) (2022) New Approach to the Detection of Short-Lived Radical Intermediates. Journal of the American Chemical Society, 144 (35). pp. 15969-15976. ISSN 0002-7863
Abstract
We report a new general method for trapping short-lived radicals, based on a homolytic substitution reaction SH2′. This departure from conventional radical trapping by addition or radical–radical cross-coupling results in high sensitivity, detailed structural information, and general applicability of the new approach. The radical traps in this method are terminal alkenes possessing a nitroxide leaving group (e.g., allyl-TEMPO derivatives). The trapping process thus yields stable products which can be stored and subsequently analyzed by mass spectrometry (MS) supported by well-established techniques such as isotope exchange, tandem MS, and high-performance liquid chromatography-MS. The new method was applied to a range of model radical reactions in both liquid and gas phases including a photoredox-catalyzed thiol–ene reaction and alkene ozonolysis. An unprecedented range of radical intermediates was observed in complex reaction mixtures, offering new mechanistic insights. Gas-phase radicals can be detected at concentrations relevant to atmospheric chemistry.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2022 The Authors. Published by American Chemical Society. This is an open access article under the terms of the Creative Commons Attribution License (CC-BY). |
Keywords: | Mixtures, Molecular structure, Organic reactions, Quantum mechanics, Redox reactions |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Physical Chemistry (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 05 Sep 2022 11:54 |
Last Modified: | 25 Jun 2023 23:05 |
Status: | Published |
Publisher: | American Chemical Society |
Identification Number: | 10.1021/jacs.2c03618 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:190485 |