DMSO‐Modulated Divergent Fluoroalcohol Addition to Alkenes via Cooperative Iron/Disulfide Photocatalysis

ABSTRACT Fluoroalcohols and their ether counterparts are indispensable pharmacophores in modern medicinal chemistry. Despite the inherent appeal of constructing these motifs through the direct addition of fluoroalcohols across alkenes, the profound inductive withdrawal exerted by the fluorine atoms engenders a formidable electronic barrier: it drastically suppresses oxygen nucleophilicity, pushes oxidation potentials to prohibitive levels, and renders the α‑C─H bonds kinetically inert. Here, we report a cooperative iron/disulfide photocatalytic framework that transcends this electronic recalcitrance through an exogenously controlled divergent strategy. By harnessing a photoinduced alkoxide to iron charge transfer (Fe‐LMCT) process, this platform bypasses traditional redox limitations to generate reactive fluoroalkoxy radicals from unactivated substrates. We further uncover a concentration‐dependent pathway regulated by DMSO: while bulk DMSO promotes a low‐barrier 1,2‐hydrogen atom transfer (HAT) of the transient fluoroalkoxy radicals to access α‐hydroxyfluoroalkyl radical reactivity, this facilitation is insufficient at additive‐level concentrations, thereby prioritizing direct O ‐centered radical reactivity. This platform provides a robust gateway to structurally complex fluorinated architectures and establishes a blueprint for orchestrating the reactivity of high‐energy radical intermediates through external chemical cues.