镍催化芳香酰胺与炔的C-H/N-H氧化环化的计算机理研究  

Computational Mechanistic Study on the Nickel-catalyzed C-H/N-H Oxidative Annulation of Aromatic Amides with Alkynes

作　　者：范伟[1] 夏亚钊 李阁[1] 张鑫[1] 李刚[1] Fan Wei;Xia Yazhao;Li Ge;Zhang Xin;Li Gang(Heze Medical College,Shandong,274000)

机构地区：[1]菏泽医学专科学校,山东274000

出　　处：《当代化工研究》2025年第3期55-57,共3页Modern Chemical Research

摘　　要：应用密度泛函理论(Density Functional Theory,DFT)计算说明Ni催化的芳香酰胺与炔的C-H/N-H氧化环化中使用的单齿链系统的反应机理。提出的反应机理包括两条反应路径:初始路径由Ni(Ⅱ)引发;催化循环由Ni(0)引发。DFT计算结果表明:初始Ni(Ⅱ)体系的速率决定步骤涉及协同金属化-去质子化过程,阴离子Ni(0)酸配合物是主催化循环的关键中间体。计算得到的不对称炔和间取代芳酰胺的区域选择性与实验结果相符。Using density functional theory(DFT)calculations to explain the reaction mechanism of the monodentate chain system used in the C-H/N-H oxidative cyclization of aromatic amides and alkynes catalyzed by Ni.The proposed reaction mechanism includes two reaction pathways:The initial pathway is initiated by Ni(Ⅱ),the catalytic cycle is initiated by Ni(0).The DFT calculation results indicate that the rate determining step of the initial Ni(Ⅱ)system involves a synergistic metalization deprotonation process,and the anionic Ni(0)acid complex is a key intermediate in the main catalytic cycle.The calculated regioselectivity of asymmetric alkynes and meta substituted aromatic amides is consistent with the experimental results.

关 键 词：密度泛函理论(DFT) Ni催化 芳香酰胺 反应机理 

分 类 号：O621.3[理学—有机化学]