Simple arenes are unconventional aryne precursors because they lack complimentary electrofugal and nucleofugal leaving groups for a redox neutral elimination event. Yet, the dehydrogenation of simple arenes represents an expansive source of latent aryne intermediates and even has the potential for late-stage functionalization of active pharmaceutical ingredients and agrochemicals. In 2023 we merged the C-H functionalization of arenes via thianthrenation and deprotonative aryne generation for a net dehydrogenation of simple arenes as an efficient way to access arynes (Scheme 1c). In our early optimization, we found that aryl thianthrenium salts were more easily accessed than aryl(Mes)iodonium salts and we therefore developed a two-step sequence in which the aryl thianthrenium salts were isolated and subsequently used as aryne precursors (Scheme 1c). Although the isolation of aryl thianthrenium salts is relatively straightforward, only involving trituration and filtration, it does represent an additional, and potentially unnecessary, manipulation (Scheme 1c). Moreover, we found gaps in scope including simple feedstocks (i.e., benzene, toluene, anisole), polysubstituted arenes (i.e., 1,3-disubstituted arenes) including heteroarenes, and several useful functional groups such as triflate, nitro, and ester (Scheme 1c). Scheme 1. Overview of access to arynes.