Given the modern challenges in public health, global food supply, environmental protection and energy efficiency, creating better molecules is imperative and we believe it is essential to make the SF5 group a prevalent part of the molecule design toolbox. In order to ensure wide and easy accessibility, SF5 compounds should be obtainable from a variety of starting materials in a synthetically efficient manner. Herein, we report how the discovery of a single-step perfluorosulfanylation of thiophenol derivatives gave rise to a convenient and generalized synthetic strategy for aryl-and heteroaryl SF5 compounds from common building blocks, such as aryl fluorides, bromides, iodides and diazonium salts, through a thiolation cross-coupling (Step 1) and oxidative fluorination (Step 2) sequence (Fig. ). As the initial puzzle piece toward our goal to increase the synthetic efficiency of pentafluorosulfanylation (Step 2), we first successfully developed a single-step oxidative fluorination of diphenyldisulfide (Ph2S2, 1) to pentafluorosulfanylbenzene (Ph-SF5, 2) using the combination of AgF2 and NEt4Cl. Our reaction development is summarized in Figure . Weak oxidants (Me-NFPy, NFSI, DBI, TBCA) did not provide sufficient reactivity and the use of Cl-NFPy, Select-F, AgF2(25), XeF2 and Br2/KF only gave phenylsulfur(IV) trifluoride (Ar-SF3). Thus, as reported in literature, the oxidative fluorination to phenylsulfur(VI) requires stronger oxidants, TCICA , Cl2/KF(9), [NEt3Me][ClF4](28) and XeF2/NEt4Cl(29) providing Ph-SF4Cl as the main product. The use of XeF2 with a soluble tetraalkylammonium salt results in stark increase in reactivity providing 2 in up to 20% yield. The use of AgF2 as the stoichiometric oxidant, as originally reported, afforded 2 from 1 only in up to 15% yield at 120 °C in 48 h. In contract, we found in this study that treatment of 1 with two equivalents NEt4Cl in the presence of an excess amount of AgF2 in acetonitrile (MeCN) provides 2 in nearly quantitative yield within a short reaction time (<1 h) at room temperature. No other products except for traces (<2%) of hydrolyzed sulfur compounds (Ph-SO2F, PhSOF) were detected. In place of NEt4Cl, other onium salts such as Bu4NCl, Et4NBr and Ph4PX (X = F, Cl, and Br) are also effective to give 2 in very high yields (see SI for details). The silver(I) byproducts (AgF, AgCl) can easily be filtered off and fluorinated back to AgF2 with industrial F2 gas.(30) Thus, the recycling of inorganic silver salts offers the potential to render the process net catalytic in AgF2 using F2 gas as the stoichiometric oxidant and fluorine source. The use of AgF2 was key for our success as the re-evaluation of suitable reagents demonstrated to us and also other high-valent metal-fluorides (e.g. CoF3, MnF3, etc.) proved to be ineffective. The equally high yield for 2 from thiophenol with slight modification of the reaction conditions (see SI for details) allowed us to investigate the substrate scope for both aryl disulfides and aryl thiols. Excellent yields for halogenated (F, Cl, Br), alkylated (Me, t Bu, CF3) or ester-containing SF5 products pointed to a high functional group compatibility. In contrast to previous methodologies, both electron-rich and electron-deficient aryl disulfides reacted equally well and gave both 3 (4-NO2) and 26 (4-OMe) in very high yields. Electron-rich thiophenols typically required longer reaction time for high yields and we account the generation of an equivalent of bifluoride (HF2 -) in the reaction medium for the deceleration the oxidative fluorination. Both paraand meta-substitution patterns were well tolerated, while ortho-substituted substrates showed diminished reactivity for the oxidation of sulfur(IV) to sulfur(VI) as observed in previous reports.