DFT Case Study on the Comparison of Ruthenium-Catalyzed C-H Allylation, C-H Alkenylation, and Hydroarylation.

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 β-H elimination steps established the following reactivity sequence of the leaving groups: protonated amide group > β-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.