Deprotection of TBS-R (3) and Rongacyl (7) were accomplished according to their literature methods. TBS-R (3) has the benefit of being a one-pot deprotection (CsF, Selectfluor). SMOPS (1) and Rongacyl ( ) requires a two-step procedure with deprotection via sodium hydride (SMOPS) and sodium hydroxide (Rongacyl) followed by workup and selectfluor addition (Table ). Given that PMB groups are generally deprotected under oxidizing conditions, we first looked for methods that would allow for selectfluor to act as the oxidant. This led to the photocatalytic deprotection of the PMB group following conditions first reported by Stephenson. Using either iridium or acridinium photocatalysis in the presence of blue light and selectfluor led directly to sulfonyl fluoride (Table , entry 2 and 3). Interestingly, however, deprotection and fluorination was able to occur (89% yield) in the absence of photocatalyst provided that three equivalents of selectfluor were present (entry 1). These conditions provide a direct, metal-free method to mildly deprotect and fluorinate PMB-R-protected aryl sulfones. Lower yields were obtained when 1 or 2 equivalents of selectfluor was used (entry 4 and 5). The presence of water is essential for the successful removal of the protecting group (entry 6). Deprotection Conditions 1. NaH 2. Yield 44% 91% 84% 86% 89% 76% based off average yield of all 10 reactions from Table . See Supporting Information for detailed conditions; temperature of the reaction is 23 °C unless otherwise noted. yields refer to isolated yield.