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dc.contributor.authorWalton, John C.
dc.identifier.citationWalton , J C 2018 , ' Reflex carbocation release from covalent molecules by endogenous free radicals ' , ACS Omega , vol. 3 , no. 10 , pp. 13290-13297 .
dc.identifier.otherPURE: 256434321
dc.identifier.otherPURE UUID: 12adb99c-9585-432a-8d90-c548cf407ad9
dc.identifier.otherScopus: 85055028475
dc.identifier.otherORCID: /0000-0003-2746-6276/work/56638742
dc.identifier.otherWOS: 000449026500109
dc.descriptionJ.C.W. thanks EaStCHEM for financial support.en
dc.description.abstractCarbocations are pervasive in contemporary organic synthesis, so new and innocuous methods of making them are always desirable. A theoretical approach revealed that compounds in which radical generation takes place may release carbocations advantageously. The radical types and molecular substructures that promote this effect were identified. The best substructures were found to be 1,3-dicarbonyl compounds, particularly those based on the Meldrum's acid theme. Sulfate esters and dithiane rings could also be employed. Radicals generated on oxygen atoms or ethyne units were particularly effective. For these species, carbocation release could be reflex, that is, concurrent with radical generation. Only small radical enhancements were observed for release of lithium cations because of the ionic character of most of the precursors. Ethyne units could be incorporated as spacers between the radical center and the site of carbocation generation. Moreover, the enhancement was transmitted down polyethyne chains of at least six units.
dc.relation.ispartofACS Omegaen
dc.rightsCopyright © 2018 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.en
dc.subjectQD Chemistryen
dc.subjectChemical Engineering(all)en
dc.titleReflex carbocation release from covalent molecules by endogenous free radicalsen
dc.typeJournal articleen
dc.description.versionPublisher PDFen
dc.contributor.institutionUniversity of St Andrews. School of Chemistryen
dc.contributor.institutionUniversity of St Andrews. EaSTCHEMen
dc.description.statusPeer revieweden

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