Cascade Amination and Acetone Monoarylation with Aryl Iodides by Palladium/Norbornene Cooperative Catalysis

A palladium/norbornene cocatalyzed three-component reaction of aryl iodides, <i>O</i>-benzoylhydroxylamines, and acetone is reported. <i>o</i>′-Aminoaryl acetones or <i>o</i>,<i>o</i>′-diaminoaryl acetones are efficiently prepared via tandem <i>ortho</i>-C–H amination/<i>ipso</i>-C–I α-arylation sequence, and the regiospecificity has been confirmed by X-ray analysis. The proposed method addresses the condensation/amination of free-<i>N</i>-H-bearing substrates in acetone monoarylations and the synthesis of extremely congested 2,6-disubstituted aryl acetones