10.1021/acs.organomet.7b00095.s001
Yi-Nuo Yang
Yi-Nuo
Yang
Ju-Long Jiang
Ju-Long
Jiang
Jing Shi
Jing
Shi
Mechanistic Study of Copper-Catalyzed Decarboxylative
C–N Cross-Coupling with Hypervalent Iodine Oxidant
American Chemical Society
2017
reductive elimination
proton transfer
Mechanistic Study
DFT
site selectivity
site-selective formation
electron transfer
reaction pathway
III
Hypervalent Iodine Oxidant Copper-catalyzed
hypervalent iodine oxidant
proton transfer process
bond
2017-05-19 17:41:18
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Mechanistic_Study_of_Copper-Catalyzed_Decarboxylative_C_N_Cross-Coupling_with_Hypervalent_Iodine_Oxidant/5026502
Copper-catalyzed directed decarboxylative
C–N cross-coupling, which is promoted by a hypervalent iodine
oxidant, provides a new strategy for the site-selective formation
of aliphatic C–N bonds. Despite the great synthetic potential,
the mechanism of this reaction and especially the origin of the radical
species still remain controversial. To resolve this problem, herein
density functional theory (DFT) calculations have been employed to
elucidate the mechanistic details of this reaction. As a result, a
comprehensive reaction pathway involving I<sup>III</sup>–O
bond heterolysis, single electron transfer (SET), hydrogen atom transfer
(HAT), decarboxylation, proton transfer, and reductive elimination
is reported. Meanwhile, analyzing the necessity of the directing groups
in realizing the site selectivity, we found that the chelation of
the directing group to the Cu(III) center can remarkably facilitate
the proton transfer process.