Photocatalyzed cycloaromatization of vinylsilanes with arylsulfonylazides

Sila-molecules have recently attracted attention due to their promising applications in medical and industrial fields. Compared with all-carbon parent compounds, the different covalent radius and electronegativity of silicon from carbon generally endow the corresponding sila-analogs with unique biological activity and physicochemical properties. Vinylsilanes feature both silyl-hyperconjugation effect and versatile reactivities, developing vinylsilane-based Smiles rearrangement will therefore provide an efficient platform to assemble complex silacycles. Here we report a practical Ir(III)-catalyzed cycloaromatization of ortho-alkynylaryl vinylsilanes with arylsulfonyl azides for delivering naphthyl-fused benzosiloles under visible-light photoredox conditions. The combination of experiments and density functional theory (DFT) energy profiles reveals the reaction mechanism involving alpha -silyl radical Smiles rearrangement. Arene-fused siloles have attracted interest due to their promising applications in electronic and optoelectronic devices. Here, the authors report Ir(III)-catalyzed cycloaromatization of ortho-alkynylaryl vinylsilanes with arylsulfonyl azides via alpha -silyl radical Smiles rearrangement for accessing naphthyl-fused benzosiloles under visible-light photoredox conditions.

Automated summary

Sila-molecules have unique biological activity and physicochemical properties compared to all-carbon compounds due to the different covalent radius and electronegativity of silicon. Vinylsilanes, featuring silyl-hyperconjugation effect and versatile reactivities, provide an efficient platform for assembling complex silacycles. The Ir(III)-catalyzed cycloaromatization of ortho-alkynylaryl vinylsilanes with arylsulfonyl azides via alpha-silyl radical Smiles rearrangement demonstrates the potential for accessing naphthyl-fused benzosiloles under visible-light photoredox conditions.