Dirhodium-catalyzed C-H arene amination using hydroxylamines

Primary and N -alkyl arylamine motifs are key functional groups in pharmaceuticals, agrochemicals, and functional materials, as well as in bioactive natural products. However, there is a dearth of generally applicable methods for the direct replacement of aryl hydrogens with NH 2 /NH(alkyl) moieties. Here, we present a mild dirhodium-catalyzed C-H amination for conversion of structurally diverse monocyclic and fused aromatics to the corresponding primary and N -alkyl arylamines using NH 2 /NH(alkyl)- O -(sulfonyl)hydroxylamines as aminating agents; the relatively weak RSO 2 O-N bond functions as an internal oxidant. The methodology is operationally simple, scalable, and fast at or below ambient temperature, furnishing arylamines in moderate-to-good yields and with good regioselectivity. It can be readily extended to the synthesis of fused N -heterocycles.