To further investigate the generality of BASN as a reductive organophotocatalyst, a high throughput reaction screening was conducted (see section 9 of SI). Good hits for reductive activation were obtained for a selection of radical precursors among which include aryl halides, benzoic esters, N-(acyloxy)phthalimides, Katritzky salt, Togni's reagent II (Tr-II), and aryl sulfonium salt (Figure ). Figure outlines examples for reductive defunctionalizations such as dehalogenations of aryl chlorides, bromides, and iodides (7a to 7c), detosylations (7e and 7f), and deoxygenations of trifluoromethylated benzoate esters (7g and 7h). Next, we turned our attention to complexity-building reactions such as transition metal-free C-C couplings of alkyl, aryl and trifluoromethyl radical precursors with olefins or heterocycles (Figure ) affording Heck-type products (8a to 8o). Interestingly, removing the base gave better yields with N-(acyloxy)phthalimides (8a to 8i) which could be attributed to a favorable catalystsubstrate preassembly via synergistic H-bond and -stacking that assisted a photoinduced intra-complex electron transferI (Figure .1, Figure for the yields with base, and section 6.12 of SI for computational investigations on these non-covalent interactions). Activation and C-heteroatom coupling of aryl chlorides was also demonstrated (Figure ) obtaining phosphorylation (9a to 9k), borylation (9l and 9m), and sulfidation (9n and 9o) products. Latestage diversification of industrially-relevant molecules (gemfibrozil 8h and 8j, caffeine 8o, boscalid 9k, and menthol 9m) and introduction of benzene bio-isosteres bicyclo[1.1.1]pentane (BCP) 8g and bicyclo[2.2.2]octane (BCO) 8f and 8i were demonstrated, further highlighting the synthetic utility of this method. In conclusion, this study outlines the underexplored third mechanistic paradigm in electron transfer photochemistryphotoredox autocatalysis. In turn, this allowed the development of BASN as a novel and generally applicable reductive organophotocatalyst architecture that is easily diversifiable and efficiently accessible in a low cost, one-pot process from anilines and sulfonyl chlorides. Due to the ubiquity of the precursors and the privileged role of sulfonamides and biaryls as robust, biocompatible motifs in medicinal chemistry, we believe this class of photocatalyst will be of great significance to chemists from industry and academia alike and may pave the way to further biological applications of BASNs. We hope that the systematic approach of this study will serve as a blueprint for further development of the budding field of photoredox autocatalysis.