Photochemical, Metal‐Free Sigmatropic Rearrangement Reactions of Sulfur Ylides

Abstract Sigmatropic rearrangement reactions constitute one of the most fundamental reactions of carbenes. While state‐of‐the‐art synthetic methods require the use of expensive precious metal catalysts, the application of visible light for the photolysis of α‐aryldiazoacetates is much less investigated and provides an operationally simple entry to carbenes under mild reaction conditions. Herein, we report on blue‐light induced sigmatropic rearrangement reactions of sulfur compounds with α‐aryldiazoacetates. This process, depending on the substitution pattern of the sulfide, opens up formal insertion reactions of carbenes into S−N, S−C, or C−H bonds.