Energy Transfer Enabled Radical Deoxygenative C(sp ³ )‐N Construction

Abstract The formation of C(sp 3 )‐N bonds constitutes a pivotal transformation in functional molecule synthesis, with conventional methods predominantly relying on polar substitution paradigms. To address the inherent limitations of existing approaches, we report a radical‐mediated strategy for sp 3 C‐N bond formation via cross‐coupling between carbon‐centered radicals and iminyl radicals. This mechanistically distinct pathway circumvents the substrate tolerance limitations associated with N ‐nucleophiles and base‐mediated side reactions. Under energy transfer catalytic conditions, oxime esters exhibit dual functionality as both N ‐radical precursors and initiators for xanthate ester‐derived carbon radicals. This synergistic activation strategy not only enhances atom economy and environmental sustainability but also results in the concurrent formation of S‐phenyl dithiocarbonate byproducts, which can serve as valuable building blocks in synthetic chemistry.