Photocatalytic Bilateral Disulfuration of Thioethers Toward <i>α</i>‐Sulfide Disulfides With Antibacterial Activity

α-Sulfide disulfides represent valuable motifs in organic and pharmaceutical chemistry. However, the limited availability of synthetic approaches for α-sulfide disulfides has impeded progress in this field. In this study, a photocatalytic approach to synthesizing modifiable α-sulfide disulfides is presented using accessible sulfides and a bilateral disulfurating reagent. The reaction proceeds under mild conditions and demonstrates broad substrate compatibility, accommodating both aromatic and aliphatic sulfides. Moreover, the synthesized α-sulfide disulfides display robust reactivity in subsequent transformations with different electrophiles. Notably, this protocol can also be applied to the modification of polymer matrices. Bioassays further reveal that certain target compounds exhibit significant antibacterial activity against plant pathogens, such as Xanthomonas oryzae pv. oryzae (Xoo), Xanthomonas oryzae pathovar oryzicola (Xoc), and Dickeya zeae (D. zeae).