Mechanism of Silver-Mediated Geminal Difluorination of Styrenes with a Fluoroiodane Reagent: Insights into Lewis-Acid-Activation Model

Fluorination mediated by the cyclic hypervalent fluoroiodane reagent (1) often requires an exogenous Lewis acid. The widely accepted Lewis-add-activation model is that a given Lewis acid binds to the oxygen atom of 1 (O-coordination) to polarize the I-O bond. Computational studies of silver-mediated geminal difluorination of styrenes with 1 reveal a new F-coordination model that is energetically much preferred over the commonly accepted O-coordination model. The calculations rationalize the regioselective formation of the geminal difluorination product.