Photoinduced Remote C(sp3)-H Imination Enabled by Vinyl Radical- Mediated 1,5-Hydrogen Atom Transfer

A vinyl radical-mediated 1,5-hydrogen atom transfer strategy for remote C(sp3)-H imination under visible-light induced photochemical metal-free conditions afforded diverse gamma- imino alkenes with excellent stereoselectivity. Oxime ester-based bifunctional reagents provided not only nucleophilic alkyl radicals for radical addition reactions with electron-deficient alkynes but also long-lived steady-state imine radicals for trapping alkyl radicals following the intramolecular 1,5-hydrogen migration of unstable olefin radicals.

Automated summary

Diverse gamma-imino alkenes with excellent stereoselectivity were synthesized through a vinyl radical-mediated 1,5-hydrogen atom transfer strategy under visible-light induced metal-free photochemical conditions. Oxime ester-based bifunctional reagents provided nucleophilic alkyl radicals for radical addition reactions with electron-deficient alkynes and long-lived steady-state imine radicals for trapping alkyl radicals following the intramolecular 1,5-hydrogen migration of unstable olefin radicals.