Fluorination technology is a core component of modern and future advances in medicine, crop protection, materials and energy conversion. While the implementation of trifluoromethyl (CF3) groups has become very popular, the less common derivatization with pentafluorosulfanyl (SF5) groupsalso referred as a super-trifluoromethyl group -very often results in superior molecular properties. In comparison to CF3, the SF5 group exhibits enhanced characteristics,(2-4) such as larger size, higher electronegativity and electron-withdrawing capacity, increased lipophilicity and can also improve hydrolytic stability (Fig. ). Thus, prominent examples for aryl SF5-compounds (Ar-SF5) outperforming their CF3-analogs can be found in all fields of molecular design, e.g. for catalysts,(5) agrochemicals,(6) materials such as liquid crystals, and in pharmaceutical chemistry. Despite the advantages of Ar-SF5 compounds, however, their widespread application is severely hampered by the cumbersome and low-yielding synthetic methodology of pentafluorosulfanylation. Initial synthetic approaches in the 1960s by Sheppard involved the direct fluorination of aryl disulfides (Ar2S2) with silver(II) difluoride (AgF2) resulting in low yield and chemoselectivity. Modern protocols proceed via a stepwise oxidative fluorination sequence involving an arylsulfur chlorotetrafluoride (Ar-SF4Cl) intermediate, which must be isolated and further converted into the SF5-product via a separate Cl-F exchange reaction (Fig. , top). The oxidative fluorination is achieved either with chlorine gas as the stoichiometric oxidant in the presence of KF, introduced by Umemoto et al. or with solid chlorinating reagent TCICA, as reported by Togni and Shibata. Due to these advances, the interest of the synthetic organic community in pentafluorosulfanylation and its related chemistry has been re-ignited recently and novel SF5-pharmaceuticals have appeared in clinical trials and patents. However, the total efficiency of the current synthetic route toward Ar-SF5 compounds remains unsatisfactory due to several associated problems: a multi-step synthetic sequence; overall low to moderate yields; difficulty in handling of intermediates due to strong smell and/or moisture sensitivity; limitations in substrate scope (e.g. for certain heterocycles and generally electron-rich arenes); long reaction time and harsh reaction conditions; limited set of available and applicable starting materials.