%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