Computational studies on hypervalent iodonium(III) compounds as activated precursors for 18F radiofluorination of electron-rich arenes

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dc.contributor.authorHill, DEen_AU
dc.contributor.authorHolland, JPen_AU
dc.date.accessioned2020-03-25T23:26:51Zen_AU
dc.date.available2020-03-25T23:26:51Zen_AU
dc.date.issued2015-08-15en_AU
dc.date.statistics2020-03-20en_AU
dc.description.abstractFluorination of deactivated and non-activated electron-rich arenes via nucleophilic aromatic substitution (SNAr) reactions represents a major challenge in medicinal and radiochemistry. In efforts to activate electron-rich arenes for facile synthesis of fluoroarenes, a wide range of reagents have been developed. In particular, aryliodonium(III) species (salts and ylides) show promise as reagents for synthesising 18F-radiolabelled molecules for use in positron emission tomography (PET). However, in fluorination reactions involving a reductive elimination mechanism, aryliodonium(III) reagents present two competing pathways that lead to product (via transition state 1 (TS1)) or by-product (TS2) formation. Here, we present detailed computational studies using Density Functional Theory (DFT) methods on the relatively stability of these competing transition states and present an analysis based on transition state theory that allows prediction of chemoselectivity in aryliodonium(III) fluorination reactions. The methods developed indicate that the calculated difference in free energy (ΔΔG‡) and the calculated equilibrium constant (ln K‡) between the two transition states are chemically accurate molecular descriptors of chemoselectivity in aryliodonium(III) fluorination. It is anticipated that the tools developed here will aid design of the next generation of reagents with increased chemoselectivity for fluorination and radiofluorination of electron-rich arenes. © 2015 Elsevier B.V.en_AU
dc.identifier.citationHill, D. E., & Holland, J. P. (2015). Computational studies on hypervalent iodonium(III) compounds as activated precursors for 18F radiofluorination of electron-rich arenes. Computational and Theoretical Chemistry, 1066, 34-46. doi:10.1016/j.comptc.2015.05.012en_AU
dc.identifier.govdoc9070en_AU
dc.identifier.issn2210-271Xen_AU
dc.identifier.journaltitleComputational and Theoretical Chemistryen_AU
dc.identifier.pagination34-46en_AU
dc.identifier.urihttps://doi.org/10.1016/j.comptc.2015.05.012en_AU
dc.identifier.urihttp://apo.ansto.gov.au/dspace/handle/10238/9244en_AU
dc.identifier.volume1066en_AU
dc.language.isoenen_AU
dc.publisherElsevier B.V.en_AU
dc.subjectComputerized simulationen_AU
dc.subjectFluorinationen_AU
dc.subjectChemical reactionsen_AU
dc.subjectDensity functional methoden_AU
dc.subjectArrhenius equationen_AU
dc.subjectDrugsen_AU
dc.subjectPositron computed tomographyen_AU
dc.titleComputational studies on hypervalent iodonium(III) compounds as activated precursors for 18F radiofluorination of electron-rich arenesen_AU
dc.typeJournal Articleen_AU
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