Anion-π Interactions in Light-Induced Reactions: Role in the Amidation of (Hetero)aromatic Systems with Activated N-Aryloxyamides

The importance of anion-pi interactions as a driving force for chemical and biological processes is increasingly being recognized. In this communication, we describe for the first time its key participation in light-induced reactions. We show, in particular, how transient complexes formed through noncovalent anion-pi interactions between electron-poor N-aryloxyamides and multiply-charged anions (such as carbonate or phosphate) can undergo facile light-promoted N-O cleavage, affording amidyl radicals that can subsequently be trapped by (hetero)aromatics.