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Computational Studies on the Mechanism of the Copper-Catalyzed sp3-C[BOND]H Cross-Dehydrogenative Coupling Reaction

Authors

  • Gui-Juan Cheng,

    1. Lab of Computational Chemistry and Drug Design, Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (P. R. China)
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  • Li-Juan Song,

    1. Lab of Computational Chemistry and Drug Design, Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (P. R. China)
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  • Dr. Yun-Fang Yang,

    1. Lab of Computational Chemistry and Drug Design, Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (P. R. China)
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  • Dr. Xinhao Zhang,

    Corresponding author
    1. Lab of Computational Chemistry and Drug Design, Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (P. R. China)
    • Lab of Computational Chemistry and Drug Design, Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (P. R. China)
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  • Prof. Dr. Olaf Wiest,

    Corresponding author
    1. Lab of Computational Chemistry and Drug Design, Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (P. R. China)
    2. Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (USA)
    • Lab of Computational Chemistry and Drug Design, Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (P. R. China)
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  • Prof. Dr. Yun-Dong Wu

    Corresponding author
    1. Lab of Computational Chemistry and Drug Design, Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (P. R. China)
    2. College of Chemistry, Peking University, Beijing 100871 (P. R. China)
    • Lab of Computational Chemistry and Drug Design, Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (P. R. China)
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Abstract

A detailed computational study of a copper-catalyzed aerobic cross-dehydrogenative coupling reaction has been conducted. To select a reliable method to describe the thermochemistry of a single electron transfer (SET) process, benchmark calculations have been performed. M06/6-311+g(d,p) is appropriate to evaluate the thermochemistry of the SET process for the system involving iminium species. The computational results support an SET mechanism, but also uncover an alternative mechanism in which O2 is directly involved in a hydrogen-abstracting step. A comparative study with tert-butylhydroperoxide (TBHP) as the oxidant has also been performed. The computations reveal several competitive pathways, including a radical pathway, a CuIII pathway, and an SET mechanism for the Cu/TBHP system.

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