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Herein, we report the identification of a photoredox autocatalytic pathway \u2010 an alternative to the existing mechanistic paradigms \u2010 to access cyclic biaryl sulfonamides (BASNs). This reaction does not require exogenous catalyst as the visible light absorbing deprotonated product \u2010 with potent excited state reductive power \u2010 acts as the photocatalyst for its own synthesis. This finding implicated BASN as a novel organophotocatalyst architecture and allowed a rapid, modular, and low\u2010cost combinatorial synthesis of a BASN library that expedited optimal photocatalyst screening. 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