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.