Catalytic Desymmetrization of 1,3‐Difluoropropan‐2‐ols via C–F Bond Activation using a Phosphazene Base Affords Monofluoromethyl‐substituted Epoxides

A facile synthetic route to monofluoromethyl substituted epoxides via the desymmetrization of 1,3-difluoropropan-2-ols is reported. A silicon-containing additive activates the inert C(sp(3))-F bond in aliphatic fluorides to promote the intramolecular epoxidation under metal-free reaction conditions. A phosphazene base, which acts as a catalyst, is indispensable for this silicon-induced defluorinative cyclization.