Ir-Catalyzed Intermolecular Branch-Selective Allylic C–H Amidation of Unactivated Terminal Olefins

An efficient method for intermolecular branch-selective allylic C–H amidation has been accomplished via Ir­(III) catalysis. The reaction proceeds through initial allylic C–H activation, supported by the isolation and crystallographic characterization of an allyl-Ir­(III) intermediate, followed by a subsequent oxidative amidation with readily available dioxazolones as nitrenoid precursors. A diverse range of amides are successfully installed at the branched position of terminal alkenes in good yields and regioselectivities. Importantly, the reaction allows the use of amide-derived nitrenoid precursors avoiding problematic Curtius-type rearrangements.