期刊
ORGANIC CHEMISTRY FRONTIERS
卷 5, 期 4, 页码 615-622出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c7qo00850c
关键词
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资金
- National Natural Science Foundation of China [21772020, 21372266]
- Fundamental Research Funds for the Central Universities (Chongqing University) [106112017CDJXY220007]
- Graduate Scientific Research and Innovation Foundation of Chongqing, China [CYB16034]
Nickel-catalyzed C-H bond activation has attracted significant attention for the construction of C-C bond frameworks. We report density functional theory investigations into the mechanism of nickel-catalyzed alkylation of benzamides with alkyl halides. Both the Ni(I)-Ni(III) and Ni(II)-Ni(IV) catalytic cycles were considered. The theoretical study indicated that the most feasible mechanism involved a Ni(II)-Ni(IV) catalytic cycle with four main steps: (i) N-H bond activation and (ii) C-H bond activation through the concerted metalation-deprotonation pathway, (iii) oxidative addition of BuBr to give a high-valent Ni(IV) complex, and (iv) C-C reductive elimination to generate the product and the active catalyst. The rate-determining step of the favored pathway is the oxidative addition, leading to the generation of a Ni(IV) intermediate. In addition, the present study casts light on the role of PPh3, which accelerates the cleavage of N-H bond. Frontier molecular orbital theory and natural population analysis were employed to explain the effect of the phosphine ligand on the structure of the Ni complex.
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