Modular Tuning of Electrophilic Reactivity of Iridium Nitrenoids for the Intermolecular Selective α‑Amidation of β‑Keto Esters

We report herein an Ir-catalyzed intermolecular amino group transfer to β-keto esters (amides) to access α-aminocarbonyl products with excellent chemoselectivity. The key strategy was to engineer electrophilicity of the putative Ir-nitrenoids by tuning electronic property of the κ²-N,O chelating ligands, thus facilitating nucleophilic addition of enol π-bonds of 1,3-dicarbonyl substrates.