Energy Transfer Enabled Radical Deoxygenative C(sp3)-N Construction

Abstract

The formation of C(sp³)-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 sp³ 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.