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

Abstract

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.

GRAPHICAL ABSTRACT

Keywords:

• Arylhydrazines
• copper catalysis
• denitrogenative arylation
• ligand-free
• phosphorylamides

Additional information

Funding

The authors are grateful for the financial support from the Fundamental Research Funds for the Key Laboratory of Research and Utilization of Ethnomedicinal Plant Resources of Hunan Province [No. YYZW2018-9] and the financial support from the Huaihua University Program [No. ZWX2016-11].