17. Intermolecular Anti-Markovnikov Hydroamination of Unactivated Alkenes with Sulfonamides Enabled by Proton-Coupled Electron Transfer

Qilei Zhu, David E. Graff, Robert R. Knowles:

https://pubs.acs.org/doi/10.1021/jacs.7b11144

ABSTRACT: Here we report a catalytic method for the intermolecular anti-Markovnikov hydroamination of unactivated alkenes using primary and secondary sulfonamides. These reactions occur at room temperature under visible light irradiation and are jointly catalyzed by an iridium(III) photocatalyst, a dialkyl phosphate base, and a thiol hydrogen atom donor. Reaction outcomes are consistent with the intermediacy of an N-centered sulfonamidyl radical generated via proton-coupled electron transfer activation of the sulfonamide N–H bond. Studies outlining the synthetic scope (>60 examples) and mechanistic features of the reaction are presented.