Photo-Electrochemical Geminal α-Fluorosulfenylation of Diazo Compounds through Carbene Radical Anion Intermediate

α-Fluorosulfenyl compounds are privileged building blocks found in pharmaceuticals and agrochemicals. While the geminal difunctionalization of diazo compounds with two different nucleophiles under mild and sustainable conditions could be envisioned as a versatile method for constructing α-fluorosulfinyl molecules, it remains a significant unmet challenge. Herein, we present geminal α,α’-difunctionalization of diazo compounds by merging photo- and electro-catalysis. A wide range of α-fluorosulfinyl products were synthesized using commercial ionic liquid as a fluorine source with moderate to good yields and excellent selectivities. Several experiments were performed to detail the reaction mechanism and elucidate the cooperativity of photo- and electro-catalysis in facilitating the reaction under milder conditions.