Clarification on the Reactivity of Diaryl Diselenides toward Hexacyclohexyldilead under Light

In this study, the reactivity of organochalcogen compounds toward a representative alkyl-lead bond compound under light was investigated in detail. Under light irradiation, the Cy-Pb bond of Cy6Pb2 (Cy = cyclohexyl) undergoes homolytic cleavage to generate a cyclohexyl radical (Cy•). This radical can be successfully captured by diphenyl diselenide, which exhibits excellent carbon-radical-capturing ability. In the case of (PhS)2 and (PhTe)2, the yields of the corresponding cyclohexyl sulfides and tellurides were lower than that of (PhSe)2. This probably occurred due to the low carbon-radical-capturing ability of (PhS)2 and the high photosensitivity of the cyclohexyl-tellurium bond.

2,2-Bis(phenylselanyl)-1-(p-tolyl)vinyl 2-Oxo-2-(p-tolyl)acetate

2,2-Bis(phenylselanyl)-1-(p-tolyl)vinyl 2-oxo-2-(p-tolyl)acetate was synthesized via the reaction of p-tolylacetylene with diphenyl diselenide and benzoyl peroxide in benzene under atmospheric conditions. The molecular structure of the synthesized compound was evaluated using single-crystal X-ray analysis and spectral analyses. The process reported here provides a rare example of the direct and selective transformation of a terminal alkyne to the corresponding geminal diseleno-substituted alkene.

Catalytic Antioxidant Activity of Bis-Aniline-Derived Diselenides as GPx Mimics

Herein, we describe a simple and efficient route to access aniline-derived diselenides and evaluate their antioxidant/GPx-mimetic properties. The diselenides were obtained in good yields via ipso-substitution/reduction from the readily available 2-nitroaromatic halides (Cl, Br, I). These diselenides present GPx-mimetic properties, showing better antioxidant activity than the standard GPx-mimetic compounds, ebselen and diphenyl diselenide. DFT analysis demonstrated that the electronic properties of the substituents determine the charge delocalization and the partial charge on selenium, which correlate with the catalytic performances. The amino group concurs in the stabilization of the selenolate intermediate through a hydrogen bond with the selenium.