Synthesis of Pentafluoroethyl Ethers by Silver-Mediated Oxidative Pentafluoroethylation of Alcohols and Phenols.

A silver triflate (AgOTf)-mediated oxidative pentafluoroethylation of alcohols and phenols with nucleophilic (pentafluoroethyl)trimethylsilane (TMSCF2CF3) using selectfluor as oxidant under mild reaction conditions was developed. This oxidative coupling protocol utilizes broadly available substrates and easily handled reagents to afford various pentafluoroethyl ethers in moderate to excellent yields. Furthermore, this method was extended to the oxidative heptafluoropropylation and ethoxycarbonyldifluoromethylation of alcohols and phenols for preparation of the corresponding fluoroalkyl ethers.