Theoretical investigation of Co(0)-catalyzed intramolecular hydroacylation of 4-pentenal.
Density functional theory (DFT) was used to investigate cobalt(0)-catalyzed intramolecular hydroacylation of 4-pentenal. The calculated results indicated the involvement of five possible reaction pathways: the formation of cyclopentanone, cyclobutanone, butylenes, cyclobutane, and cyclopropane, respectively. The former two are pathways of Co(0)-catalyzed intramolecular hydroacylation, while the latter three are pathways of decarbonylation. The formation of cyclopentanone was the most favorable channel, and the oxidative addition reaction of 4-pentenal was the rate-determining step. Hence, the dominant product predicted theoretically was cyclopentanone, which was consistent with experimental results. Solvation had a significant effect, and greatly decreased the free energies of all intermediates and transition states.
College of Chemistry and Material Science, Shandong Agricultural University, Taian, Shandong 271018, People's Republic of China. qingxim@sdau.edu.cn
Qingxi
Q
Meng
Fen
F
Wang
Ming
M
Li