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.