Molecular dynamics simulation study of post‐transition state bifurcation: A case study on the ambimodal transition state of dipolar/Diels–Alder cycloaddition

Abstract

AbstractThe potential energy surfaces for the reactions of 1,3‐butadiene with 2‐hydroxythioacrolein and 2‐aminoacrolein exhibit ambimodal transition states leading to both dipolar (4 + 3) and Diels–Alder (4 + 2) cycloaddition products, thereby demonstrating a post transition state bifurcation feature. We have investigated the bifurcation dynamics of these reactions using three molecular dynamics (MD) methods: quasi‐classical trajectory, classical MD, and ring‐polymer MD simulations. The trajectory calculations were performed with the semiempirical GFN2‐xTB method with the element‐specific parameters optimized to reproduce the density‐functional theory calculations. The effect of water solvation was examined using an implicit solvation model, revealing significant differences in bifurcation dynamic between gas‐phase and solution‐phase reactions. Nuclear quantum effects were found to play a crucial role in the proton‐transfer process from the (4 + 3) intermediate to the (4 + 3) product in the case of the 2‐aminoacrolein reaction.