Amidyl radical-mediated aminodifluoroallylation of alkenes via photoredox catalysis

Nitrogen-containing heterocycles are prevalent in both natural and synthetic bioactive molecules. We report herein an unprecedented protocol for the radical aminodifluoroallylation of alkenes with pendent N-aryl amides via synergistic photoredox and Bronsted base catalysis, furnishing gem-difluoroalkene-containing N-heterocycles with high diversity. The reaction proceeds through a cascade of PCET (proton-coupled electron transfer)-based amidyl radical formation, 5-exo cyclization, coupling with trifluoromethyl alkenes, and beta-fluoride elimination. Moreover, this transformation exhibits wide functional-group compatibility and occurs under redox-neutral conditions.

Automated summary

This study presents a novel method for the radical aminodifluoroallylation of alkenes with pendent N-aryl amides using synergistic photoredox and Bronsted base catalysis, leading to the synthesis of gem-difluoroalkene-containing N-heterocycles with high diversity. The reaction mechanism involves a cascade of PCET-based amidyl radical formation, 5-exo cyclization, coupling with trifluoromethyl alkenes, and beta-fluoride elimination, demonstrating wide functional-group compatibility and redox-neutral conditions.