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    Mechanistic Insight into the Photoredox-Nickel-HAT Triple Catalyzed Arylation and Alkylation of α-Amino Csp3–H Bonds

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    Revised_Csp3-H_Manuscript_R3-2020-08-16.pdf
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    Description:
    Accepted manuscript
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    Type
    Article
    Authors
    Maity, Bholanath cc
    Zhu, Chen cc
    Yue, Huifeng
    Huang, Long
    Harb, Moussab cc
    Minenkov, Yury
    Rueping, Magnus cc
    Cavallo, Luigi cc
    KAUST Department
    KAUST Catalysis Center (KCC)
    Physical Science and Engineering (PSE) Division
    Chemical Science Program
    Date
    2020-09-09
    Online Publication Date
    2020-09-09
    Print Publication Date
    2020-10-07
    Embargo End Date
    2021-09-09
    Permanent link to this record
    http://hdl.handle.net/10754/665080
    
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    Abstract
    We report here a comprehensive computational analysis of the mechanisms of the photoredox-nickel-HAT (HAT: hydrogen atom transfer) catalyzed arylation and alkylation of α-amino Csp3–H bonds developed by MacMillan and coworkers. Different alternatives for the three catalytic cycles were tested to identify unambiguously the operative reaction mechanism. Our analysis indicated that the IrIII photoredox catalyst, upon irradiation with visible light, can be either reduced or oxidized by the HAT and nickel catalysts, respectively, indicating that both reductive and oxidative quenching catalytic cycles can be operative, although the reductive cycle is favored. Our analysis of the HAT cycle indicated that activation of a α-amino Csp3‒H bond of the substrate is facile and selective relative to activation of a β-amino Csp3‒H bond. Finally, our analysis of the nickel cycle indicated that both arylation and alkylation of α-amino Csp3–H bonds occurs via the sequence of nickel oxidation states NiI-NiII-NiI-NiIII, and of elementary steps: radical addition-SET-oxidative addition-reductive elimination.
    Citation
    Maity, B., Zhu, C., Yue, H., Huang, L., Harb, M., Minenkov, Y., … Cavallo, L. (2020). Mechanistic Insight into the Photoredox-Nickel-HAT Triple Catalyzed Arylation and Alkylation of α-Amino Csp3–H Bonds. Journal of the American Chemical Society. doi:10.1021/jacs.0c05010
    Sponsors
    We acknowledge King Abdullah University of Science and Technology (KAUST) for support and the KAUST Supercomputing Laboratory for providing computational resources of the supercomputer Shaheen II.
    Publisher
    American Chemical Society (ACS)
    Journal
    Journal of the American Chemical Society
    DOI
    10.1021/jacs.0c05010
    Additional Links
    https://pubs.acs.org/doi/10.1021/jacs.0c05010
    ae974a485f413a2113503eed53cd6c53
    10.1021/jacs.0c05010
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

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