As part of ongoing efforts in this laboratory to design and synthesize multidentate soft-N-donors as effective complexants for chemoselective minor actinide extraction from used nuclear fuel, a series of aminated mono-1,2,4-triazinylpyridines were required. This study focuses on streamlining convergent access to a diverse array of functionalized N-donors using Pd-catalysis from a common synthon affording access to pyridinyl triazines as the 4,4'-amino derivatives which are commercially limited and unsuccessful in traditional condensation chemistry. A general Pd-catalyzed method for the double amination of functionalized pyridinyl-1,2,4-triazines with low catalyst/ligand loadings enabling the formation of 16 novel complexants is presented.

Pd-Catalyzed Diamination of 1,2,4-Triazinyl Complexant Scaffolds. -A Pd-catalyzed reaction of bis(bromophenyl) substituted 1,2,4-triazines (I) with primary amines (II) is developed to yield novel 4,4'-bisaminophenyl substituted monotriazinylpyridine derivatives (III) as potential ligands for chemoselective minor actinide extraction processes. -(TAI, S.; DOVER, E. J.; MARCHI, S. V.; CARRICK*, J. D.; J. Org. Chem. 80 (2015) 12, 6275-6282, http://dx.doi.org/10.1021/acs.joc.5b00710 ; Dep. Chem., Tenn. Technol. Univ., Cookeville, TN 38505, USA; Eng.) -Mais 44-196