Molecular dynamics of bicyclo[2.2.0]hex-2-ene ring opening and its polar derivative: allowed vs. forbidden pathways

Abstract

We employed density functional theory, CCSD(T) and CASSCF computations, along with quasi-classical molecular dynamics simulations, to explore the ring opening of bicyclo[2.2.0]hex-2-ene and its 1-amino-4-cyano derivative. While the overall reaction is a formally forbidden 4-electron disrotatory electrocyclization, both conrotatory and disrotatory pathways operate for the hydrocarbon, the latter involving a HOMO–LUMO crossing and diradical transition state. Quasi-classical simulations reveal the presence of non-statistical dynamic behavior involving a short-lived intermediate in the formally forbidden process. For the donor/acceptor-substituted derivative, the charge separation induced by substitution eliminates orbital symmetry restrictions, enabling a sterically favored disrotatory pathway.