Despite ample evidence for the unique reactivity offered by hypervalent F-iodanes, mechanistic investigations fall far behind. In order to shed light on the unusual behavior of such F-reagents, we conducted computational and experimental studies on the chemodivergent transformation of styrenes. We identified the spirocyclic F-cyclopropane as the common intermediate for both the C, H-fluorination and C, H-amination pathways. The fate of this key compound is determined by the extent of cationic charge delocalization controlled by the N-substituents. Exploiting this phenomenon, a multitude of different transformations have become available, leading, i.e., to the regiodivergent synthesis of indoles and tryptophans.

Fluorination reactions facilitated by hypervalent F‐iodanes have experienced vivid attention recently, since they often lead to novel, fluorinated scaffolds not accessible with common electrophilic fluorination reagents. The fluorocyclization of styrenes equipped with an amide functionality in the ortho position using F‐iodanes represents a transformation with unusual chemoselectivity. Within this context, the conversion of pyridine derivatives to fluoropyridyloxazepines, which constitutes a particular challenge due to the deactivating properties of the aza heterocycle, was accomplished in this work using the bench‐stable λ3‐F‐benzoiodoxole under Lewis acid catalysis. The versatility of the obtained F‐heterocycles as building blocks in organic synthesis was demonstrated by their straightforward conversion into azaindoles in a one‐pot, three‐step reaction sequence.