Sulfur (VI) fluoride exchange (SuFEx) click chemistry has emerged as a valuable tool in organic synthesis and biochemistry . Notably, sulfamoyl fluorides have increasingly become pivotal building blocks in the SuFEx domain due to their unique properties, including chemical stability and selective reactivity at the sulfur center . Recently, researchers have utilized sulfamoyl fluorides as efficient linkers to facilitate the assembly of sulfonyl derivatives, such as sulfamides, sulfonamides, and sulfamates (Figure , left). The distinctive reactivity of sulfamoyl fluoride is anticipated to streamline the challenges associated with the multi-step synthesis of sulfonyl derivatives , thereby garnering significant attention towards the synthesis of sulfamoyl fluorides. Methods have been developed for rapid construction of sulfamoyl fluoride moiety (Figure , right), including the chloride-fluoride exchange of sulfamoyl chlorides , Hofmann rearrangement of sulfonamides . In contrast to the aforementioned S-F bond formation, electrophilic fluorosulfonyl reagents such as fluorosulfuryl imidazolium salt , phenyl] imidodisulfuryl difluoride (AISF) , and sulfuryl fluoride (SO2F2) can react with amines to provide a straightforward method for the synthesis of sulfamoyl fluorides. Furthermore, synthetic building blocks containing the sulfamoyl fluoride group, such as fluorosulfuryl isocyanate (FSI) , N-(fluorosulfonyl)carbamate and its lithium salt , and N-fluoro-N-(fluorosulfonyl) carbamate (NFC) , can efficiently react with various reaction receptors to prepare the corresponding products.