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

Org Lett. 2016 Dec 2;18(23):6128-6131. doi: 10.1021/acs.orglett.6b03134. Epub 2016 Nov 17.

Abstract

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.

Publication types

  • Research Support, Non-U.S. Gov't