Synthesis of New Sulfonyloximes and Their Use in Free-Radical Olefin Carbo-oximation

New bifunctional reagents for free-radical carbo-oximation of olefins have been developed. In this process, a single reagent can act both as a trap for nucleophilic radicals as well as a source of electrophilic radical via an α-scission of an alkylsulfonyl radical. This strategy involving the addition of a C-centered electrophilic radical and an oxime across the double bond of an electron-rich alkene is initiated with a t-BuO radical following an unusual mechanism, supported by both experiments and density functional theory calculations.