Journal
ACS OMEGA
Volume 7, Issue 7, Pages -Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsomega.1c06584
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Funding
- National Natural Science Foundation of China [22003045, 21773010]
- Fundamental Research Funds for Tianjin Colleges [2018KJ171]
- High-Performance Computing Platform of Tianjin Chengjian University
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Density functional calculations were carried out to understand the mechanism of ruthenium-catalyzed C-H allylation. The study reveals the sequential processes involved in the reaction and identifies the rate-determining step as C-H activation. Additional calculations explored other reaction pathways between arenes and alkenes.
Density functional calculations at the B3LYP-D3+IDSCRF/TZP-DKH(-dfg) level of theory have been performed to understand the mechanism of ruthenium-catalyzed C-H allylation reported in the literature in depth. The plausible pathway consisted of four sequential processes, including C-H activation, migratory insertion, amide extrusion, and recovery of the catalyst, in which C- H activation was identified as the rate-determining step. The amide extrusion step could be promoted kinetically by trifluoroacetic acid since its mediation lowered the free-energy barrier from 32.1 to 12.2 kcal/mol. Additional calculations have been performed to explore other common pathways between arenes and alkenes, such as C-H alkenylation and hydroarylation. A comparison of the amide extrusion and beta-H elimination steps established the following reactivity sequence of the leaving groups: protonated amide group > beta-H group > unprotonated amide group. The suppression of hydroarylation was attributed to the sluggishness of the Ru-C protonation step as compared to the amide extrusion step. This study can unveil factors favoring the C-H allylation reaction.
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