期刊
CHEMCATCHEM
卷 13, 期 15, 页码 3536-3542出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cctc.202100672
关键词
Amide C-N activation; Nickel catalysis; Structure-activity relationship; Distortion; interaction analysis; DFT calculations
资金
- National Natural Science Foundation of China [21702182, 21873081]
- Fundamental Research Funds for the Central Universities [2020XZZX002-02]
- State Key Laboratory of Clean Energy Utilization [ZJUCEU2020007]
- Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University
This study elucidates the controlling factors of Ni/PCy3-catalyzed amide C-N bond activation barrier using density functional theory calculations and distortion/interaction analysis. It is found that substrate distortion is the key factor that differentiates amide reactivity, leading to two distinctive structure-activity relationships for planar and twisted amides. Moreover, the understanding of the structure-activity relationship provides a rational and predictive basis for future reaction designs involving transition metal-catalyzed amide C-N bond activation.
Transition metal-catalyzed amide C-N bond activation has emerged as a powerful strategy to utilize amides in synthetic transformations. The key mechanistic basis for the rational design of amide reagents is the structure-activity relationship of amide C-N bond activation. In this work, the controlling factors of Ni/PCy3-catalyzed amide C-N bond activation barrier are elucidated with density functional theory (DFT) calculations and distortion/interaction analysis. We found that the substrate distortion is the key factor that differentiates the amide reactivity in the C-N bond activation. The substrate distortion of amide is associated with two distinctive structure-activity relationships. The general planar amides undergo a classic three-membered ring oxidative addition to cleave the C-N bond, in which the C-N heterolytic bond dissociation energy has a linear relationship with the activation barrier. The twisted amides have a chelation-assisted transition state for the amide C-N bond cleavage, and the twisted angle tau can serve as a predictive parameter for the reactivity of the twisted amides. The understanding of the structure-activity relationship of amide C-N bond activation provides a rational and predictive basis for future reaction designs involving transition metal-catalyzed amide C-N bond activation.
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