DFT Studies on the Dirhodium-Catalyzed [3 + 2] and [3 + 3] Cycloaddition Reactions of Enol Diazoacetates with Isoquinolinium Methylide: Mechanism, Selectivity, and Ligand Effect Shi-Jun Li De-Cai Fang 10.1021/acs.organomet.8b00069.s002 https://acs.figshare.com/articles/dataset/DFT_Studies_on_the_Dirhodium-Catalyzed_3_2_and_3_3_Cycloaddition_Reactions_of_Enol_Diazoacetates_with_Isoquinolinium_Methylide_Mechanism_Selectivity_and_Ligand_Effect/6194828 The reaction mechanisms of dirhodium-catalyzed [3 + 2] and [3 + 3] cycloaddition between enol diazoacetate and isoquinolinium methylide have been studied in detail using density functional theory and a solution-phase translational entropy model. The reaction starts with the formation of a metallic carbene intermediate first, from which two competing reaction channels of [3 + 2] and [3 + 3] cycloaddition take place. For <b>CAT1</b>-catalyzed reactions, the calculated activation free energy barriers for [3 + 3] and [3 + 2] cycloaddition reactions are 14.3 and 16.0 kcal mol<sup>–1</sup>, respectively, which is in good agreement with the ratio of products. Both the steric and electronic effects have been considered for <b>CAT2</b>- and <b>CAT3</b>-catalyzed reactions, with which the ratio of products has also been rationalized. 2018-04-27 14:40:13 reaction channels energy barriers reaction mechanisms cycloaddition DFT Studies enol diazoacetate Isoquinolinium Methylide CAT 1 CAT 3 solution-phase translational entropy model Ligand Effect Enol Diazoacetates CAT 2 isoquinolinium methylide