Iron-Catalyzed Radical Asymmetric Aminoazidation and Diazidation of Styrenes

Asymmetric aminoazidation and diazidation of alkenes are straightforward strategies to build value-added chiral nitrogen-containing compounds from feedstock chemicals. They provide direct access to chiral organoazides and complement enantioselective diamination. Despite the advances in non-asymmetric reactions, asymmetric aminoazidation or diazidation based on acyclic systems has not been previously reported. Here we describe the iron-catalyzed intermolecular asymmetric aminoazidation and diazidation of styrenes. The method is practically useful and requires relatively low loading of catalyst and chiral ligand. With mild reaction conditions, the reaction can be completed on a 20 mmol scale. Studies of the mechanism suggest that the reaction proceeds via a radical pathway and involves stereocontrol of an acyclic free radical which probably takes place through a group transfer mechanism.

Automated summary

This study reports the iron-catalyzed intermolecular asymmetric aminoazidation and diazidation of styrenes, providing a direct and efficient pathway for constructing chiral nitrogen-containing compounds. The method shows potential value in the synthesis of chiral organoazides, with relatively low loading of catalyst and chiral ligand required for practical application.