Superacid BF3–H2O promoted benzylation of arenes with benzyl alcohols and acetates initiated by trace water

Abstract

A convenient procedure employing simple starting materials benzyl alcohols and acetates as the benzyl donors to assemble a series of diarylalkanes through benzylation of arenes using in situ prepared superacid BF₃–H₂O as an efficient promoter has been developed. The beneficial role of water in the reaction has been clarified with combination of control experiments and ¹¹B NMR analysis. This reaction is a self-promoted model, which is triggered by the trace of water and continuously promoted by self released by-product water (or carboxylic acid). A wide range of substrates are investigated and the moderate to excellent yields and the good regioselectivities for secondary benzyl alcohols as well as arenes bearing electron-withdrawing groups have been achieved. As a result, moisture in the reaction system has been utilized as an efficient initiator in all benzylation cases.