Temperature Dependent Divergent Radical Oxidative Amidation Engaging Arylglyoxyl Radicals

The present study reports the divergent reaction of previously underexplored arylglyoxyl radicals generated <i>in situ</i> from arylglyoxals in the presence of <i>tert</i>-butyl hydroperoxide (TBHP) and a catalytic amount of iodine with various amines at two different temperatures leading to the synthesis of arylglyoxal amides at 120 °C and aromatic amides at 180 °C. The two radicals, arylglyoxyl radical and aroyl radical, generated via decarbonylation at higher temperature, could react with amines via radical polar crossover.