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 NH₂/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 NH₂/NH(alkyl)-O-(sulfonyl)hydroxylamines as aminating agents; the relatively weak RSO₂O-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.