Dynamic Diselenide Bonds: Exchange Reaction Induced by Visible Light without Catalysis.(Hot Paper)

Shaobo Ji, Wei Cao, Ying Yu, and Huaping Xu

Angew. Chem. Int. Ed., 2014, 53, 6781-6785.

Dynamic covalent bonds are extensively employed in dynamic combinatorial chemistry. The metathesis reaction of disulfide bonds is widely used, but requires catalysis or irradiation with ultraviolet (UV) light. It was found that diselenide bonds are dynamic covalent bonds and undergo dynamic exchange reactions under mild conditions for diselenide metathesis. This reaction is induced by irradiation with visible light and stops in the dark. The exchange is assumed to proceed through a radical mechanism, and experiments with 2,2,6,6-tetramethylpiperidin-1-yloxyl (TEMPO) support this assumption. Furthermore, the reaction can be conducted in different solvents, including protic solvents. Diselenide metathesis can also be used to synthesize diselenide-containing asymmetric block copolymers. This work thus entails the use of diselenide bonds as dynamic covalent bonds, the development of a dynamic exchange reaction under mild conditions, and an extension of selenium-related dynamic chemistry.