Enhanced Basicity of Ag₂O by Coordination to Soft Anions

Abstract

Abstract In Ag 2 O‐mediated benzylation, the addition of a catalytic amount of KI can greatly improve reactivity. This is usually attributed to the formation of a more reactive iodo‐substituted electrophile. However, our studies show this to be due to the enhanced basicity of Ag 2 O through coordination of soft iodide anions to the silver atom, and show KI to be an initiator. A catalytic amount of Ag 2 O and NaBr can catalyze transesterification reactions, indicating the enhanced basicity of Ag 2 O by bromide. We believe that this is a general effect for metal oxides and soft anions, applicable to a wider range of organic reaction systems.