Light Illuminates Polarity-Mismatched Cycloaddition to Convert Isoquinoliniums into Phenylnaphthyl Sulfones

A visible-light-driven skeletal editing strategy that converts readily available isoquinolinium salts into phenylnaphthyl sulfones via a formal CN-to-CC atom-pair swap is presented. The process is triggered by an isoquinolinium-carbonate electron donor-acceptor (EDA) complex that, upon blue-light excitation, undergoes single-electron transfer to initiate a polarity-mismatched (4 + 2) radical annulation with alkynyl sulfones. The reaction proceeds at room temperature without external photocatalysts, tolerates diverse functional groups (including halides), and furnishes the targeted diarylsulfones with high efficiency.