The current work focuses on the DFT calculation of the rational mechanism and catalytic activity of the gold(i)-catalyzed isotetradehydro-Diels-Alder cycloaddition of cyanamides and enamides to substituted 2,6-diaminopyridines. IPrAuCl is used as a model catalyst to catalyze cyanamide and enynamide reactants with different substituents in DCM as a research system. DFT data indicates that the catalytic cycle starts from the triple bond coordination between the catalyst's gold cation and the enamide to obtain the gold π-complex, and the cyanamide attacks the alkynyl carbon atom from different directions to generate two reaction channels of five-membered and six-membered heterocycles, respectively. The calculation results show that the 2,6-diaminopyridine compounds produced by this catalytic reaction have lower activation energy and higher reactivity, that is, the pyridine skeleton structure can be easily obtained under mild reaction conditions. At the same time, electron-withdrawing substituents in the reactants are more helpful for the reaction. In addition to being in good agreement with the experimental data, the calculated results also provide an important contribution to the further understanding of the mechanism of such reactions.
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