Ligand-free copper-catalyzed denitrogenative arylation of phosphorylamides with arylhydrazines

A straightforward arylation of phosphorylamides with arylhydrazines hydrochloride was herein demonstrated. The protocol proceeded in the presence of a catalytic loading of Cu(OAc)2 as the catalyst, DTBP as the external oxidant and Cs2CO3 as the base, but without any ligands. And a series of N-aryl phosphorylamides were successfully obtained in high efficiency (up to 93% yields) with good substituents compatibility (up to 30 examples). Free radical mechanism was proposed for the facile methodology based on the results of control reactions and literature explorations.