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.

Keywords: carbenes; diazoalkanes; metal-free reactions; photochemistry; rearrangements.