Versatile method for the synthesis of aminobenziodoxolones and its application to one-pot coupling of arylboronic acids with simple amines

Abstract

Hypervalent iodine(III) compounds containing transferable nitrogen functional groups, amino-λ³-iodanes, were synthesized via a straightforward protocol utilizing simple amines and a benziodoxolone framework. This strategy enabled the use of a wide variety of amines, including ammonia, aliphatic and aromatic primary amines, significantly expanding the scope of accessible compounds compared to existing methods. The synthesized aminobenziodoxolones were applied to the oxidative amination of arylboronic acids, offering a practical transition-metal-free protocol for the synthesis of arylamines. To further demonstrate the synthetic utility, a one-pot process using in-situ prepared aminobenziodoxolones was developed, allowing efficient coupling of boronic acids with various simple and pharmaceutically relevant amines. Furthermore, the method was extended to the synthesis of ¹⁵N-labelled arylamines, highlighting the versatility and practical value of this approach.