Visible-Light-Driven α-Substituted Amines Enabled by In Situ Formation of Amine Substrate Aggregates.

A visible-light-driven, photocatalyst-free, air-promoted, α-substituted reaction of amines with varying nucleophiles is described. The amine substrate aggregates formed in situ through physical π-π stacking by H 2 O regulation in organic solvent can absorb visible light and then generate iminium ion intermediates, which undergo nucleophilic substitution reactions with varying nucleophiles to afford α-substituted amines. This reaction features catalyst-free, good functional group tolerance, simple operation procedure, and green reaction conditions.