Williams, Peter J.H., Boustead, Graham A., Heard, Dwayne E. et al. (3 more authors) (2022) New Approach to the Detection of Short-Lived Radical Intermediates. Journal of the American Chemical Society. 15969−15976. ISSN 1520-5126
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. Funding Information: This study was supported by the Engineering and Physical Sciences Research Council Doctoral Training Partnership award EP/N509802/1. We thank J. F. Hamilton and T. J. Dillon for helpful discussions and E. Bergstrom (York Centre of Excellence for Mass Spectrometry) for advice and assistance with running MS instruments. K. A. Read is thanked for help with ozone instruments and calibration at York. |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Depositing User: | Pure (York) |
Date Deposited: | 12 Sep 2022 13:10 |
Last Modified: | 06 Feb 2025 00:10 |
Published Version: | https://doi.org/10.1021/jacs.2c03618 |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1021/jacs.2c03618 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:190946 |