Herein, we describe an efficient and mild route to arynes from simple arenes via a two-step formal dehydrogenation reaction (Scheme 1c). Specifically, site-selective aryne formation is enabled by the regioselective installation and ejection of an "onium" leaving group. Synthetically useful halide substituents are compatible and fully retained in this strategy, 7,8,9 and aryne formation occurs at a remote site to the halide. We demonstrate that aryne formation occurs with a range of aryl substituents and substitution patterns and arynophiles. Moreover, the two-step process can be "telescoped" in a single pot and is amenable to late-stage functionalization of approved drugs (Scheme 1c, clofibrate). Finally, we highlight the novelty of this approach by showing that aryne intermediates provide access to regioisomer products that are distinct from other methods.