14. Mechanistic study on the regioselectivity of Co-catalyzed hydroacylation of 1,3-dienes
Density functional theory (DFT) method was used to explore the origin of the regioselectivity of Cocatalyzed hydroacylation of 1,3-dienes. The reaction of 2-methyl-1,3-butadiene and benzaldehyde with 1,3-bis(diphenylphosphino)propane ligand was chosen as the model reaction. The energies of the intermediates and transition states in the stages of oxidative cyclization, b-H elimination and C-H reductive elimination were investigated. Computational results show that b-H elimination is the ratedetermining step for the whole catalytic cycle. C1-Selective oxidative cyclization is favored over C4- selective oxidative cyclization. Besides, C4-selective oxidative cyclization is kinetically disfavored than all the steps in C1-hydroacylation mechanisms, consistent with the experimentally obtained C1- selective hydroacylation products. Analyzing the reason for such observation, we suggest that both electronic and steric effects contribute to the C1-selectivity. On the electronic aspect, C1 is more
2024-04-23