American Chemical Society
ol6b03134_si_001.pdf (1.05 MB)

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

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journal contribution
posted on 2016-11-17, 18:37 authored by Biying Zhou, Taishan Yan, Xiao-Song Xue, Jin-Pei Cheng
Fluorination mediated by the cyclic hypervalent fluoroiodane reagent (1) often requires an exogenous Lewis acid. The widely accepted Lewis-acid-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.