Selective Intramolecular CH Amination through the Metalloradical Activation of Azides: Synthesis of 1,3‐Diamines under Neutral and Nonoxidative Conditions

N2 is the only by-product in a stereospecific and highly diastereoselective intramolecular CH amination of sulfamoyl azides with a cobalt(II)-based metalloradical catalyst (see scheme). The catalytic system has an unusual capacity for the efficient amination of strong primary CH bonds, as well as secondary and tertiary CH bonds, and functional-group tolerance is excellent owing to the neutral and nonoxidative conditions.