Palladate Precatalysts for the Formation of C–N and C–C Bonds

A series of imidazolium-based palladate precatalysts has been synthesized and the catalytic activity of these air- and moisture-stable complexes evaluated as a function of the nature of the imidazolium counterion. These precatalysts can be converted under catalytic conditions to Pd-NHC species capable of enabling the Buchwald–Hartwig aryl amination and the α-arylation of ketones. Both reactions can be carried out efficiently under very mild operating conditions. The effectiveness of the protocol was tested on functionality-laden substrates.