Oxime ester as bifunctional reagent for the alkylamination of alkynes via C-centered radical addition and N-centered radical migration

The radical addition/functional group migration strategy has emerged as a powerful tool for the difunctionalization of unsaturated hydrocarbons, yet the heteroatom-mediated functional group migration remains largely unexplored. Herein, we report an unprecedented radical difunctionalization of alkynes employing oxime esters as bifunctional reagents through a novel C-centered radical addition/N-centered radical translocation sequence. This innovative transformation paradigm enables efficient alkylamination of alkynes under mild photocatalytic redox conditions. Mechanistic investigations reveal a cascade sequence initiated by single-electron transfer from oxime derivatives, proceeding through radical addition, 6-exo-trig cyclization, and subsequent imino group migration.