Synthesis and Structure of Hypervalent Diacetoxybromobenzene and Aziridination of Olefins with Imino-λ<sup>3</sup>-bromane Generated in Situ under Metal-Free Conditions

Ligand exchange of <i>p</i>-CF<sub>3</sub>C<sub>6</sub>H<sub>4</sub>BrF<sub>2</sub> with acetoxy groups using AcOH and Ac<sub>2</sub>O affords (diacetoxybromo)benzene in a high yield, which undergoes aziridination of alkenes in the presence of TfNH<sub>2</sub> and sulfamate esters in one pot under mild conditions. The aziridination with TfNH<sub>2</sub> proceeds stereospecifically with retention of stereochemistry of olefins at room temperature using limiting amounts of olefins under transition-metal-free conditions. The one-pot aziridination procedure using sulfamate esters can be applied to the intramolecular versions.