期刊
SCIENCE
卷 377, 期 6612, 页码 1323-+出版社
AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/science.abq8663
关键词
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资金
- EPSRC [EP/P004997/1]
- European Research Council [758427]
- Leverhulme Trust
- CNRS
- ANR [220424]
This work presents a distinct reactivity mode enabled by quantum mechanical tunneling using a cyclohexadiene derivative as the abstractor under mild photochemical conditions. Experimental and computational studies reveal a noncanonical pathway for activation of various organic compounds.
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.
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