A Proline-Based 'Redox-Release' Platform for Programmed Access to Diverse Sulfur(VI) and Fluoroalkyl Radicals.

Radical identity is traditionally coupled to the strategy required for its generation, necessitating distinct precursor classes and activation modes to furnish different reactive intermediates. Here, we introduce a modular redox-release platform that provides programmable access to diverse S(VI) and fluoroalkyl radicals from a common proline-derived scaffold, decoupling the radical identity from precursor activation. Complementary oxidative and reductive activation pathways converge on a shared α-amino radical intermediate to furnish chemically distinct radicals. The platform exhibits broad utility in hydrofunctionalization, late-stage functionalization, synthetic diversification, and target-oriented synthesis, while mechanistic and computational studies suggest a common β-scission pathway underlying its generality. More broadly, redox-release establishes a strategy in which activation mode and radical identity become independent design parameters for radical generation.