Ether Cleavage Re‐Investigated: Elucidating the Mechanism of BBr₃‐Facilitated Demethylation of Aryl Methyl Ethers

One of the most well‐known, highly utilized reagents for ether cleavage is boron tribromide (BBr 3 ), and this reagent is frequently employed in a 1:1 stoichiometric ratio with ethers. Density functional theory calculations predict a new mechanistic pathway involving charged intermediates for ether cleavage in aryl methyl ethers. Moreover, these calculations predict that one equivalent of BBr 3 can cleave up to three equivalents of anisole, producing triphenoxyborane [B(OPh) 3 ] prior to hydrolysis. These predictions were validated by gas chromatography analysis of reactions where the BBr 3 :anisole ratio was varied. Not only do we confirm that sub‐stoichiometric equivalents may be used for ether demethylation, but the findings also support our newly proposed three cycle mechanism for cleavage of aryl methyl ethers.