The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 19, 2024

The mechanism of the dirhodium-catalyzed combined C–H functionalization/Cope rearrangement (CH/Cope) reaction discovered by Davies group has been investigated with density functional theory (DFT) calculations and quasi-classical molecular dynamics (MD) simulations. Computations from previously showed that there is a post-transition state bifurcation leading to direct CH also CH/Cope product. While this work was in preparation, Tantillo Ess independently reported quantum mechanical studies on dirhodium-tetracarboxylate-catalyzed diazoester insertion reactions 1,3-cyclohexadiene 1,4-cyclohexadiene, respectively. cited "dynamic mismatching" explain origins low yield products some experiments; explained product selectivity perspective TS vibrational modes their synchronization occurs at entropic intermediates. We report trajectories for carbene 1-methylcyclohexene afford both products. After passing through transition involves mostly hydrogen transfer, momentum drives toward

Language: Английский