Accessing radical intermediates by photo-induced single electron transfer (SET) is dominated by two popular strategies: i) photoredox catalysis, where a catalytic chromophore is used to harvest energy from light to induce SET events and ii) photocatalyst-free reactions such as irradiation of visible light absorbing substrates or electron donor and acceptor (EDA) complexes , where stoichiometric reagents are involved (Figure , left). Both have their own advantages and drawbacks. For example, the former strategy enjoys the redox activation of non-photo absorbing substrates but requires an initial effort of screening appropriate photocatalysts which are often expensive or can require elaborate synthesis. On the other hand, the latter strategy boasts a green and cost-effective alternative (as it is photocatalyst free) but requires reactants to either be sufficiently photo-absorbing or electronically biased such that they form photo-absorbing complexes. Unbeknownst to many, there is a process that has the intermediary characteristics of the two, whereby no external photocatalyst is needed at the start of the reaction but as the product accumulates, the reaction accelerates . As such, it inherits both the assets of the aforementioned popular pathways. This third process is called photoredox autocatalysis, where an intermediate or a product of a reaction acts as the photocatalyst for its own formation (Figure , right). Thermally, autocatalysis is an important process found in biochemical pathways and is often attributed as the primordial method to access chirality . Moreover, this was observed in organo-zinc reactions (i.e., Soai reaction) , cycloadditions , directed ortholithiation , and supramolecular chemistry . However, autocatalysis has thus far enjoyed limited attention and practical applications in the field of synthetic photochemistry therefore the need to fill this knowledge gap is apparent and timely. In recent years, organophotocatalysts have proven to be a viable alternative to traditional precious transition-metal photocatalysts. In line with this, many research groups aspire to design an organophotocatalyst scaffold that is easy to prepare and has desirable photophysical and redox properties . Inspired by the prominence of sulfonamides in medicinal chemistry, due to their rigidity and exceptional chemical/metabolic stability, we reasoned that sulfonamide containing moieties would be good candidates for inexpensive, stable photocatalyst frameworks. Interestingly, the sulfonamidyl functionality in photocatalyst structure is unprecedented as its reactivity mainly involves the applications of N-centered radicals (i.e. as hydrogen atom transfer, HAT, agents) which require a preliminary oxidation step (e.g. Hofmann-Löffler type reaction, proton coupled electron transfer, photochemical or electrochemical oxidation) . Nevertheless, the ease of sulfonamidyl anion oxidation is an attractive starting point for a catalyst design (Figure , left). Intuitively, incorporation of aryl groups as chromophores at sulfonamide's nitrogen and sulfonyl groups would make the compound photoactive in the UV-B/A region (Figure , top right). Furthermore, we posited that by simply connecting these aryl groups as a cyclic biaryl sulfonamide (henceforth abbreviated as BASN) might set up a push-pull extended  electronic system shifting the absorption to the visible region. With this catalyst design at hand and considering that BASNs themselves are emerging bioactive compounds (Figure , bottom right), we sought to investigate BASN's synthetic and catalytic potential.