Mild C─F Activation of Azido(per)Fluoroalkanes

In this study, we explore a new approach for the mild and selective activation of C(sp 3 )–F bonds in fluorinated azidoalkanes. Our approach utilizes electrophilic azide groups, which promote fluoride elimination and enable nucleophilic addition to newly formed electrophilic sites. This method achieves rapid, high‐yield transformations of (per)fluoroalkyl azides into novel sulfur‐containing azides, imines, and triazoles under mild conditions and using inexpensive reagents. The reaction proceeds without metal catalysts or external energy input and displays broad functional group tolerance, including toward thiol‐sensitive motifs. Mechanistic studies supported by spectroscopy and x‐ray crystallography, corroborated by ab initio calculations, reveal key azide intermediates and establish the denitrogenation pathway via α,α‐disubstituted species. This transformation provides a practical and scalable route for the conversion of (per)fluoroalkyl azides into nitrogen‐ and sulfur‐functionalized scaffolds, advancing C─F activation processes.