Chemoselective Primary Amination of Aryl Boronic Acids by PIII/PV═O-Catalysis: Synthetic Capture of the Transient Nef Intermediate HNO

A catalytic approach to intercept the transient HNO for a chemoselective primary amination of arylboronic acids is reported. A phosphetane-based catalyst operating within PIII/PV═O redox cycling is shown to capture HNO, generated in situ by Nef decomposition of 2-nitropropane, to selectively install the primary amino group at aryl Csp2 centers. The method furnishes versatile primary arylamines from arylboronic acid substrates with the preservation of otherwise reactive functional groups.