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.
Fields of Study & Subjects
Cyclization and Aryne Chemistry
Advanced Chemical Physics Studies
Organic Chemistry Cycloaddition Reactions
Publication details
- Journal / source
- Chemical Science
- Publisher
- Royal Society of Chemistry (RSC)
- Volume
- 17
- Issue
- 13
- Pages
- 6644–6652
- Publication date
- 1 January 2026
- Language
- EN