Iron-Catalyzed Site-Selective γ-C(sp ³ )-H Azidation of Hydroxylamine Derivatives

We report an iron-catalyzed intermolecular C(sp³)-H azidation that proceeds with exclusive γ-selectivity relative to the carbonyl group via a 1,5-hydrogen atom transfer process initiated by an iron-nitrenoid species. This strategy, based on the combination of hydroxylamine derivatives and trimethylsilyl azide with a simple iron catalyst, provides efficient access to a broad range of azido-amide and azido-carbamate products.