Buchwald–Hartwig Amination of Nitroarenes

The Buchwald-Hartwig amination of nitroarenes was achieved for the first time by using palladium catalysts bearing dialkyl(biaryl)phosphine ligands. These cross-coupling reactions of nitroarenes with diarylamines, arylamines, and alkylamines afforded the corresponding substituted arylamines. A catalytic cycle involving the oxidative addition of the Ar-NO2 bond to palladium(0) followed by nitrite/amine exchange is proposed based on a stoichiometric reaction.