Harnessing Bifunctional <i>N</i> ‐Benzoyloxyamides for Photoredox Amidative Dual Functionalizations of Alkenes

Abstract Here, we present a photocatalytic strategy for the intermolecular dual functionalizations of alkenes using N─O bifunctional reagents in an atom‐economical fashion. By leveraging N ‐benzoyloxyamides as bifunctional precursors for generating both amidyl radical and internal O‐nucleophiles, this approach achieves chemoselective olefin amidation with simultaneous incorporation of additional functional groups. The current method readily accesses a range of doubly functionalized amino products through 1,2‐amidooxygenation, amidoazidation, and formal anti ‐Markovnikov hydroamidation. Mechanistic studies revealed that the selective interplay of radical and ionic pathways is operative to enable a unified platform for this olefin dual functionalization.