biostudies-literatureZhang YDivision of ChemistryFundamental Research Funds for the Provincial Universities of ZhejiangNational Natural Science Foundation of ChinaProvince-Ministry Co-Construct State Key Laboratory of Green Chemistry-Synthesis Technology at Zhejiang University of TechnologyNational Institute of General Medical SciencesNIGMS NIH HHS17176-17186https://www.ebi.ac.uk/biostudies/studies/S-EPMC12442840biostudies-literatureUnknown89(23)The mechanism of the dirhodium-catalyzed combined C-H functionalization/Cope rearrangement (CH/Cope) reaction discovered by the Davies group has been investigated with density functional theory (DFT) calculations and quasi-classical molecular dynamics (MD) simulations. Computations from the Davies group previously showed that there is a post-transition state bifurcation leading to a direct CH reaction and also to the CH/Cope product. While this work was in preparation, the Tantillo group and the Ess group independently reported quantum mechanical and molecular dynamics studies on the dirhodium-tetracarboxylate-catalyzed diazoester CH/Cope and CH insertion reactions with 1,3-cyclohexadiene and 1,4-cyclohexadiene, respectively. The Tantillo group cited "dynamic mismatching" to explain the orThe Journal of organic chemistryMolecular Dynamics of the Davies Ambimodal C-H Functionalization/Cope Rearrangement Reaction.PMC12442840223712562213801121978272RF-C2022006CHE-2153972R01 GM099142GM099142Yang YFDavies HMLZhang YCao CHouk KNShe YfalseMolecular Dynamics of the Davies Ambimodal C-H Functionalization/Cope Rearrangement Reaction.The mechanism of the dirhodium-catalyzed combined C-H functionalization/Cope rearrangement (CH/Cope) reaction discovered by the Davies group has been investigated with density functional theory (DFT) calculations and quasi-classical molecular dynamics (MD) simulations. Computations from the Davies group previously showed that there is a post-transition state bifurcation leading to a direct CH reaction and also to the CH/Cope product. While this work was in preparation, the Tantillo group and the Ess group independently reported quantum mechanical and molecular dynamics studies on the dirhodium-tetracarboxylate-catalyzed diazoester CH/Cope and CH insertion reactions with 1,3-cyclohexadiene and 1,4-cyclohexadiene, respectively. The Tantillo group cited "dynamic mismatching" to explain the or2024-01-01T00:00:00Z2024 Dec2026-06-03T12:08:24.022Z2026-04-27T03:11:18.222ZS-EPMC124428403956067110.1021/acs.joc.4c01682