The article presents a novel method for the reductive difunctionalization of alkenes using iron-catalyzed radical-anion relay, facilitated by Na₂S₂O₄ as both a reductant and sulfone source. This approach overcomes the limitations of traditional metal-catalyzed reactions, which require stoichiometric amounts of metal reductants and directing groups to suppress β-H elimination. The mechanism involves the formation of carbon-centered alkyl radicals and sulfur-centered alkyl sulfone radicals, which are in equilibrium via capture or extrusion of SO₂. Iron electron-shuttle catalysis accelerates the conversion of these radicals to alkyl sulfone anions, leading to high chemoselectivity. The method is demonstrated through the successful synthesis of a variety of acyclic and cyclic sulfones, including valuable scaffolds in material science, medicinal chemistry, and natural products. The scope of the methodology is broad, encompassing various olefins, alkyl halides, and functional groups, with high yields and regioselectivity. The synthetic versatility of the method is further illustrated through the preparation of intermediates for the synthesis of Erysolin and its fluorinated derivatives, a CYP1A inhibitor. Mechanistic studies support the proposed radical-anion relay pathway, confirming the role of Na₂S₂O₄ and iron catalysts in the reaction.The article presents a novel method for the reductive difunctionalization of alkenes using iron-catalyzed radical-anion relay, facilitated by Na₂S₂O₄ as both a reductant and sulfone source. This approach overcomes the limitations of traditional metal-catalyzed reactions, which require stoichiometric amounts of metal reductants and directing groups to suppress β-H elimination. The mechanism involves the formation of carbon-centered alkyl radicals and sulfur-centered alkyl sulfone radicals, which are in equilibrium via capture or extrusion of SO₂. Iron electron-shuttle catalysis accelerates the conversion of these radicals to alkyl sulfone anions, leading to high chemoselectivity. The method is demonstrated through the successful synthesis of a variety of acyclic and cyclic sulfones, including valuable scaffolds in material science, medicinal chemistry, and natural products. The scope of the methodology is broad, encompassing various olefins, alkyl halides, and functional groups, with high yields and regioselectivity. The synthetic versatility of the method is further illustrated through the preparation of intermediates for the synthesis of Erysolin and its fluorinated derivatives, a CYP1A inhibitor. Mechanistic studies support the proposed radical-anion relay pathway, confirming the role of Na₂S₂O₄ and iron catalysts in the reaction.