Halogen‐Bonding‐Induced Direct SET Activation of Aryl Iodides: Inorganic Bases as Self‐Sufficient Electron Donors

Aryl radicals are traditionally generated via single‐electron transfer (SET) mediated by transition metals or photoredox catalysts. While XB‐mediated electron donor–acceptor complexes offer a catalyst‐free alternative, they typically require exogenous organic additives. Herein, we report an “additive‐free” paradigm where aryl radicals are directly generated from aryl iodides via SET from ubiquitous inorganic bases under mild light‐emitting diode (LED) irradiation. This streamlined approach bypasses external donors, enabling efficient conversion into aryl boronic esters, stannanes, and heteroarenes. Our findings unveil the hidden potential of simple bases as potent photo‐reductants via XB, offering a sustainable breakthrough for radical chemistry.