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