Electronic effects of ruthenium-catalyzed [3+2]-cycloaddition of alkynes and azides

D.-R. Hou, T.-C. Kuan, Y.-K. Li, R. Lee, K.-W. Huang
Tetrahedron, volume 66, issue 48, 9415-9420, (2010)

Electronic effects of ruthenium-catalyzed [3+2]-cycloaddition of alkynes and azides

Keywords

Ruthenium-catalyzed azide-alkyne cycloaddition

Abstract

​A combined experimental and theoretical study of ruthenium-catalyzed azide-alkyne cycloaddition (RuAAC) reactions is presented and various electronic analyses were conducted to provide a basis in understanding the observed regioselectivity of the 1,2,3-triazole products. Computational studies using density functional theory (DFT) and atoms in molecules quantum theory (AIM) further yield fresh details on the electronic factors that determine the regioselectivity in the RuAAC. It is found that the formation of 1,2,3-triazole products is irreversible and from the Hammett study, the pathway involving a vinyl cationic intermediate is ruled out. The electronic effect favors the formation of 5-electron-donating-group substituted-1,2,3-trizoles.

Code

DOI: 10.1016/j.tet.2010.09.099

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