Photoredox Catalyzed Dealkylative Aromatic Halogen Substitution with Tertiary Amines.

A reaction of aromatic halides bearing electron-withdrawing groups with tertiary amines in the presence of an iridium catalyst under blue light irradiation is described. Products of the aromatic substitution of the halide by the dialkylamino fragment are obtained. The interaction of aryl radicals with tertiary amines to generate zwitterionic radical species is believed to be the key factor responsible for the reaction efficiency.

Flexible Synthesis of Phosphoryl-Substituted Imidazolines, Tetrahydropyrimidines, and Thioamides by Sulfur-Mediated Processes.

The solvent-free sulfur-mediated reactions of phosphinic chlorides with alkyl diamines were developed for the practical synthesis of unknown phosphoryl-substituted 4,5-dihydro-1H-imidazoles, 1,4,5,6-tetrahydropyrimidines, and thioamides. Their good tolerance to functional groups, broad substrate scope, and easy scalability were shown. The chemoselective preparation of a variety of phosphoryl-substituted bis(thioamides) was accomplished via the adjustment of a solvent.