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

Abstract

A silver triflate (AgOTf)-mediated oxidative pentafluoroethylation of alcohols and phenols with nucleophilic (pentafluoroethyl)trimethylsilane (TMSCFCF) 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.

Recent Advances in the Application of Selectfluor as a “Fluorine‐free” Functional Reagent in Organic Synthesis

“…In this process, TMSC2F5, TMSCF2CO2Et, TMSCH2CF2CF3 and phenols were found to be effective substrates for the preparation of the corresponding fluoroalkyl ethers (Scheme 1b). [10] A plausible reaction mechanism was also reported, depicted in Scheme 1c. In the presence of AgOTf, 2-fluoropyridine, and KF, TMSCF3 could be converted into Ag(I)CF3.…”

“…[4] Besides, other transition metal catalysts, such as, Ag, Cu, Fe and Pd could also be well oxidized by Selectfluor and applied in different organic synthesis. [10][11][12][13][14][15][16][17][18][19][20][21] In 2015, Qing and coworkers reported a novel method for the construction of alkyl trifluoromethyl ethers through Ag-promoted oxidative trifluoromethylation of alcohols with TMSCF3 in the presence of Selectfluor (Scheme 1a). [9] Following this study, the same group updated the reaction system to broaden the substrate scope.…”

Silver(i) Perfluoroalcoholates: Synthesis, Structure, and their Use as Transfer Reagents

“…The authors have cited additional references within the Supporting Information. [47][48][49][50][51][52][53][54] Deposition…”