Kristof T. J. Loones, B. Maes, W. Herrebout
Apr 30, 2007
Citations
0
Influential Citations
17
Citations
Journal
Tetrahedron
Abstract
Abstract The intramolecular amination of N -(3-bromopyridin-2-yl)azaheteroarylamines and N -(2-chloropyridin-3-yl)azaheteroarylamines was investigated. In this way we unraveled the mechanism of the ring closure reaction in the auto-tandem amination (inter- and intramolecular Pd-catalyzed amination) of 2,3-dibromopyridine with amino(benzo)(di)azines and 2-chloro-3-iodopyridine with amino(benzo)(di)azines, respectively. Depending on the substrate a Pd-catalyzed amination, a base-assisted nucleophilic aromatic substitution or a combination of both is occurring. An explanation based on the aromaticity of the amidine, supported by theoretical calculations, is provided. In addition we gained evidence that the intramolecular metal-catalyzed amination of N -(3-bromopyridin-2-yl)azaheteroarylamines and N -(2-chloropyridin-3-yl)azaheteroarylamines indeed involves a nitrogen atom that is not substituted with a hydrogen atom.