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Halogen-atom and group transfer reactivity enabled by hydrogen tunnelling

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dc.contributor.authorConstantin, Timothee
dc.contributor.authorGorski, Bartosz
dc.contributor.authorTilby, Michael J.
dc.contributor.authorChelli, Saloua
dc.contributor.authorJuliá Hernández, Fabio
dc.contributor.authorLlaveria, Josep
dc.contributor.authorGillen, Kevin J.
dc.contributor.authorZipse, Hendik
dc.contributor.authorLakhdar, Sami
dc.contributor.authorLeonori, Daniele
dc.contributor.departmentQuímica Inorgánica
dc.date.accessioned2025-01-24T11:33:25Z
dc.date.available2025-01-24T11:33:25Z
dc.date.issued2022-09-16
dc.description© 2022 the authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ This document is the Accepted Manuscript version of a Published Work that appeared in final form in Science. To access the final edited and published work see https://doi.org/10.1126/science.abq8663
dc.description.abstractThe generation of carbon radicals by halogen-atom and group transfer reactions is generally achieved using tin and silicon reagents that maximize the interplay of enthalpic (thermodynamic) and polar (kinetic) effects. In this work, we demonstrate a distinct reactivity mode enabled by quantum mechanical tunneling that uses the cyclohexadiene derivative γ-terpinene as the abstractor under mild photochemical conditions. This protocol activates alkyl and aryl halides as well as several alcohol and thiol derivatives. Experimental and computational studies unveiled a noncanonical pathway whereby a cyclohexadienyl radical undergoes concerted aromatization and halogen-atom or group abstraction through the reactivity of an effective H atom. This activation mechanism is seemingly thermodynamically and kinetically unfavorable but is rendered feasible through quantum tunneling.
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dc.format.extent22
dc.identifier.citationScience, 2022, Vol. 377, Issue 6612, pp. 1323-1328
dc.identifier.doihttps://doi.org/10.1126/science.abq8663
dc.identifier.issnPrint: 0036-8075
dc.identifier.issnElectronic: 1095-9203
dc.identifier.urihttp://hdl.handle.net/10201/149268
dc.languageenges
dc.publisherAmerican Association for the Advancement of Science
dc.relationD. L. thanks EPSRC for a Fellowship (EP/P004997/1), the European Research Council for a research grant (758427) and the Leverhulme Trust for additional support (Philip Leverhulme Prize); S. L. thanks CNRS and ANR (PhotoFlat N°220424) for financial support.es
dc.relation.publisherversionhttps://www.science.org/doi/10.1126/science.abq8663
dc.rightsinfo:eu-repo/semantics/openAccesses
dc.rightsAttribution-NonCommercial-NoDerivatives 4.0 Internacional*
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/*
dc.titleHalogen-atom and group transfer reactivity enabled by hydrogen tunnellinges
dc.typeinfo:eu-repo/semantics/articlees
dspace.entity.typePublicationes
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