%0 Generic %A Li, Shi-Jun %A Fang, De-Cai %D 2018 %T DFT Studies on the Dirhodium-Catalyzed [3 + 2] and [3 + 3] Cycloaddition Reactions of Enol Diazoacetates with Isoquinolinium Methylide: Mechanism, Selectivity, and Ligand Effect %U 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 %R 10.1021/acs.organomet.8b00069.s002 %2 https://acs.figshare.com/ndownloader/files/11224499 %K reaction channels %K energy barriers %K reaction mechanisms %K cycloaddition %K DFT Studies %K enol diazoacetate %K Isoquinolinium Methylide %K CAT 1 %K CAT 3 %K solution-phase translational entropy model %K Ligand Effect %K Enol Diazoacetates %K CAT 2 %K isoquinolinium methylide %X 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 CAT1-catalyzed reactions, the calculated activation free energy barriers for [3 + 3] and [3 + 2] cycloaddition reactions are 14.3 and 16.0 kcal mol–1, respectively, which is in good agreement with the ratio of products. Both the steric and electronic effects have been considered for CAT2- and CAT3-catalyzed reactions, with which the ratio of products has also been rationalized. %I ACS Publications