Finally, we showcased a telescope synthesis of 2a directly from commercially-available o-iodoaniline 4 and tosyl chloride 5 without much erosion of yield (73%) compared to the single-step process. Considering BASN -'s photophysical and reductive properties (vide supra), we investigated its use as a photocatalyst. We chose reductive de-functionalization of aryl halides methyl 2-chlorobenzoate (-2.00 V vs SCE) and 4-bromobiphenyl (-2.4 V vs SCE) as our model reactions. Taking advantage of the successful telescope synthesis of BASN and to expedite the determination of the best BASN structure for reductive de-functionalization, a combinatorial catalyst screening approach was designed whereby nine building blocks (i.e., five sulfonyl chlorides and four iodo-anilines) were used to assemble a library of 20 BASN structures in parallel by telescoped sulfonamide synthesis and photoredox autocatalytic cyclization (Figure ). Subsequently, the reductive de-functionalization of aryl halides was tested in these in situ generated photocatalysts and the results are outlined in Figure . While all 20 catalyst structures performed well with the activated aryl chloride substrate (yield 81 to >99%, see SI, Figure ), the variation in catalytic performance was more pronounced when model substrate 4-bromobiphenyl was used which has a deeper reduction potential. Here, the best performing photocatalyst is BASN 2b. We recognize exploiting the generation of arylradicals from aryl iodides followed by intramolecular cyclization (Figure ). Examples include six-membered methylated biaryl sultams (3a and 3b), and biaryl sultones (3c to 3e). Keeping in mind pharmaceutically-relevant ring systems, we synthesized novel seven-membered cyclic biaryl variants (3f to 3l) and assembled spirocyclic structures via a cascade of aryl radical generation followed by 1,5-HAT and then radical cyclization (6a to 6k).