Publication: Halogen-atom and group transfer reactivity enabled by hydrogen tunnelling
Authors
Constantin, Timothee ; Gorski, Bartosz ; Tilby, Michael J. ; Chelli, Saloua ; Juliá Hernández, Fabio ; Llaveria, Josep ; Gillen, Kevin J. ; Zipse, Hendik ; Lakhdar, Sami ; Leonori, Daniele
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Publisher
American Association for the Advancement of Science
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DOI
https://doi.org/10.1126/science.abq8663
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info:eu-repo/semantics/article
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
Abstract
The 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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Citation
Science, 2022, Vol. 377, Issue 6612, pp. 1323-1328
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