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 g-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.
Item Type: | Journal article |
---|---|
Faculties: | Chemistry and Pharmacy > Department of Chemistry |
Subjects: | 500 Science > 540 Chemistry |
ISSN: | 0036-8075 |
Language: | English |
Item ID: | 111385 |
Date Deposited: | 02. Apr 2024, 07:25 |
Last Modified: | 02. Apr 2024, 07:25 |