Dehydroxylative Fluorination of Tertiary Alcohols

A large number of fluorination methods have been developed, but the construction of a tertiary C-F bond remains challenging. Herein, we describe an efficient dehydroxylative fluorination of tertiary alcohols with Selectfluor via the activation of a hydroxyl group by a Ph₂PCH₂CH₂PPh₂/ICH₂CH₂I system. Although the reagents appear to be not compatible (Selectfluor with the phosphine and I^- generated in situ), the reactions occur rapidly to give the desired products in moderate to high yields. This work may present a new discovery in fluorination of alcohols since the reported methods are mainly limited to primary and secondary alcohols.