The copper catalysed reaction of sodium methoxide with aryl bromides. A mechanistic study leading to a facile synthesis of anisole derivatives

Abstract

The copper catalysed reaction of unactivated aryl bromides with sodium methoxide has been investigated by studying a number of parameters (copper catalyst, cosolvent, concentration and relative ratio of the reactants, additives and aryl bromide substituents) which influence this reaction. The ipso-substitution reaction was found to proceed via an intimate electron transfer mechanism involving a cuprate-like intermediate, Na[Cu(OMe){2}]. A convenient synthesis of methyl aryl ethers from aryl bromides and concentrated sodium methoxide solutions in dimethyl formamide and methanol is presented. Also an attempt to extend this reaction to the use of chlorine derivatives was made.