Halogen-atom and group transfer reactivity enabled by hydrogen tunneling

Timothée Constantin, Bartosz Górski, Michael J. Tilby, Saloua Chelli, Fabio Julia Hernandez, Josep Llaveria, Kevin J. Gillen, Hendrik Zipse, Sami Lakhdar, Daniele Leonori

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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. Herein, we demonstrate a distinct reactivity mode enabled by quantum mechanical tunnelling that uses the cyclohexadiene derivative -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 non-canonical pathway whereby a cyclohexadienyl radical undergoes concerted aromatization and halogen-atom/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 tunnelling.
Original languageEnglish
Pages (from-to)1323-1328
Issue number6612
Early online date15 Sep 2022
Publication statusPublished - 16 Sep 2022


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