Oxidative coupling of methylamine with an aminyl radical: direct amidation catalyzed by I2/TBHP with HCl.

Oxidative coupling of methylamines with an aminyl radical to construct amides was developed in the presence of an I-2/TBHP catalyst under acidic conditions via the two cleavages of the sp(3) C-N bond of aryl-methylamines and the sp(2) C-N bond of N-substituted formamides respectively. This transition-metal-free protocol provides a novel synthetic tool for the construction of N-substituted amides and a series of arylamides can be easily obtained with good yields.