PCET-Enabled Olefin Hydroamidation Reactions with N‑Alkyl Amides

Olefin aminations are important synthetic technologies for the construction of aliphatic C–N bonds. Here we report a catalytic protocol for olefin hydroamidation that proceeds through transient amidyl radical intermediates that are formed via proton-coupled electron transfer (PCET) activation of the strong N–H bonds in N-alkyl amides by an excited-state iridium photocatalyst and a dialkyl phosphate base. This method exhibits a broad substrate scope, high functional group tolerance, and amenability to use in cascade polycyclization reactions. The feasibility of this PCET protocol in enabling the intermolecular anti-Markovnikov hydroamidation reactions of unactivated olefins is also demonstrated.