Iron-Catalyzed Selective Etherification and Transetherification Reactions Using Alcohols

[Image: see text] Simple and readily available iron(III) triflate turned out to be a cheap, environmentally benign, and efficient catalyst for the direct etherification of alcohols. The use of ammonium chloride as an additive (5 mol %, 1 equiv relative to catalyst) suppressed the side reactions completely and ensured the selective ether formation even on challenging substrates containing electron-donating substituents. This method allows the selective synthesis of symmetrical ethers from benzylic secondary alcohols and unsymmetrical ethers directly from secondary and primary alcohols. Moreover, transetherification of symmetrical ethers using primary alcohols is attained. The reaction progress of symmetrical ether and unsymmetrical ether formation followed zero-order and first-order kinetics, respectively. Electron paramagnetic resonance (EPR) measurements of the reaction mixture and simple iron(III) triflate clearly indicated that oxidation state of the metal center remains same throughout the catalysis. Mechanistic studies confirmed that the unsymmetrical ether formation occurs via the in situ formed symmetrical ethers.