A new iron-catalyzed method for the reductive difunctionalization of alkenes with two different alkyl halides is reported. The reaction uses sodium dithionite (Na₂S₂O₄) as both a reductant and a sulfone source, enabling the formation of alkyl sulfone anions instead of traditional alkylmetal intermediates. This approach avoids the need for directing groups and reduces the use of metal reductants, improving atom economy and environmental friendliness. The mechanism involves a radical-anion relay, where a carbon-centered radical is captured by a sulfur-centered radical, leading to the formation of an alkyl sulfone anion. This anion then reacts with another alkyl halide to produce the desired product. The reaction shows high chemoselectivity and tolerance for various functional groups, including alkene, ester, ketone, and aromatic rings. The method was tested with a wide range of alkenes and alkyl halides, yielding diverse sulfones, including cyclic and valuable bioactive compounds. The reaction was also applied to synthetic applications, such as the functionalization of products and the synthesis of Erysolin and its derivatives. Mechanistic studies confirmed the role of Na₂S₂O₄ and iron as electron shuttles, enabling the formation of the desired products through a radical-anion relay pathway. This work demonstrates the potential of electron-shuttle catalysis in improving the efficiency and selectivity of reductive difunctionalization reactions.A new iron-catalyzed method for the reductive difunctionalization of alkenes with two different alkyl halides is reported. The reaction uses sodium dithionite (Na₂S₂O₄) as both a reductant and a sulfone source, enabling the formation of alkyl sulfone anions instead of traditional alkylmetal intermediates. This approach avoids the need for directing groups and reduces the use of metal reductants, improving atom economy and environmental friendliness. The mechanism involves a radical-anion relay, where a carbon-centered radical is captured by a sulfur-centered radical, leading to the formation of an alkyl sulfone anion. This anion then reacts with another alkyl halide to produce the desired product. The reaction shows high chemoselectivity and tolerance for various functional groups, including alkene, ester, ketone, and aromatic rings. The method was tested with a wide range of alkenes and alkyl halides, yielding diverse sulfones, including cyclic and valuable bioactive compounds. The reaction was also applied to synthetic applications, such as the functionalization of products and the synthesis of Erysolin and its derivatives. Mechanistic studies confirmed the role of Na₂S₂O₄ and iron as electron shuttles, enabling the formation of the desired products through a radical-anion relay pathway. This work demonstrates the potential of electron-shuttle catalysis in improving the efficiency and selectivity of reductive difunctionalization reactions.