Exploring Diradical Chemistry: A Carbon‐Centered Radical May Act as either an Anion or Electrophile through an Orbital Isomer |
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| Authors: | Dr. Théo P. Gonçalves Dr. Mubina Mohamed Prof. Richard J. Whitby Dr. Helen F. Sneddon Prof. David C. Harrowven |
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| Affiliation: | 1. Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ (UK);2. GlaxoSmithKline, Stevenage, Hertfordshire, SG1 2NY (UK) |
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| Abstract: | Diradical intermediates, formed by thermolysis of alkynylcyclobutenones, can display radical, anion, or electrophilic character because of the existence of an orbital isomer with zwitterionic and cyclohexatrienone character. Our realization that water, alcohols, and certain substituents can induce the switch provides new opportunities in synthesis. For example, it can be used to shut down radical pathways and to give access to aryl carbonates and tetrasubstituted quinones. |
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| Keywords: | density functional calculations flow chemistry radicals rearrangements small ring systems |
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