Iodoarene-Catalyzed Stereospecific Intramolecular sp3 C–H Amination: Reaction Development and Mechanistic Insights

A new strategy is reported for intramolecular sp3 C–H amination under mild reaction conditions using iodoarene as catalyst and m-CPBA as oxidant. This C–H functionalization involving iodine­(III) reagents generated in situ occurs readily at sterically hindered tertiary C–H bonds. DFT (M06-2X) calculations show that the preferred pathway involves an iodonium cation intermediate and proceeds via an energetically concerted transition state, through hydride transfer followed by the spontaneous C–N bond formation. This leads to the experimentally observed amination at a chiral center without loss of stereochemical information.