Oxidative α-Amination and Aziridination of Cyclic β-Ketoesters Using Aminobenziodoxolones

The oxidative amination of β-ketoesters with hypervalent iodine reagents bearing transferable amino groups (aminobenziodoxolones) is described. NH₂-substituted and alkylamine-derived aminobenziodoxolones enable electrophilic α-amination, whereas the use of arylamine-derived reagents promotes aziridination to afford fused aziridines. The developed methods expand the scope of accessible α-amino-β-ketoester scaffolds, which represent unique and valuable synthetic intermediates for the construction of nitrogen-containing compounds.