From Lone Pairs to Power Players: How Non-nucleophilic Lone Pairs Can Control the Nucleophilicity of a Catalyst

A lone pair-π interaction was employed to alter the reactivity of three isochalcogenourea catalysts in a model silylation reaction. Even though a lone pair-π interaction is a relatively weak interaction, working cooperatively with a bond-forming step allowed the interaction to alter the reactivity of the catalyst over the inherent nucleophilicity in an alcohol silylation reaction.