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Dynamic Intermediates in the Radical Cation Diels–Alder Cycloaddition: Lifetime and Suprafacial Stereoselectivity

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journal contribution
posted on 09.05.2018, 00:00 by Jacqueline S. J. Tan, Viivi Hirvonen, Robert S. Paton
Cation radical Diels–Alder cycloadditions proceed via an acyclic intermediate that exists on a flat region of the potential energy surface. Competition between cyclization and C–C bond rotation results in varying levels of suprafacial stereoselectivity. Quasi-classical trajectories were used to explore reaction dynamics on this surface. Even though there is no discernible energy barrier toward cyclization, a dynamically stepwise process is found, for which the acyclic intermediate is found to reside for several hundreds of femtoseconds. In a small number of cases, exceptionally long lifetimes (>1000 fs) are found, leading to a loss of alkene stereochemistry.