Computational Mechanistic Study on the Nickel-Catalyzed C–H/N–H Oxidative Annulation of Aromatic Amides with Alkynes: The Role of the Nickel (0) Ate Complex

DOI Web Site 被引用文献6件 参考文献64件
  • Ken Yamazaki
    Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
  • Atsushi Obata
    Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
  • Akane Sasagawa
    Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
  • Yusuke Ano
    Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
  • Naoto Chatani
    Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan

書誌事項

公開日
2018-12-27
資源種別
journal article
DOI
  • 10.1021/acs.organomet.8b00684
公開者
American Chemical Society (ACS)

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説明

Density functional theory (DFT) was used to unveil intimate mechanistic insights on the monodentate-chelation system that is used in the Ni-catalyzed C–H/N–H oxidative annulation of aromatic amides with alkynes, a reaction that was originally reported by our group  Chem Sci. 2017, 8, 6650−6655, DOI: 10.1039/C7SC01750B). The proposed reaction mechanism involves two reaction paths. The initial path is initiated by Ni(II), and the other, the main catalytic cycle, is initiated by Ni(0). Both paths require the presence of a catalytic amount of KOBut. The results of the DFT studies presented here indicate that the rate-determining step in the initial Ni(II) system involves a concerted metalation–deprotonation (CMD) mechanism and an anionic Ni(0) ate complex is the key intermediate in the main catalytic cycle. Furthermore, a previously proposed oxidative addition–alkyne insertion sequence is revised to a ligand-to-ligand hydrogen transfer (LLHT) mechanism, which is the rate-determining step in the main catalytic...

収録刊行物

  • Organometallics

    Organometallics 38 (2), 248-255, 2018-12-27

    American Chemical Society (ACS)

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