The utility of the products with sulfamoyl fluoride group was demonstrated (Figure ). Based on our prior research, we discovered that phenylsulfamoyl fluoride can readily undergo facile elimination to form azasulfene intermediates , facilitated by the acidic nature of the N-sulfamoyl proton. These intermediates can then be captured by amines to yield the corresponding sulfamides . Along this line, we prepared the corresponding sulfamoyl fluoride products 3a' and 7g' (in situ, not isolated), and then directly added the corresponding amines including benzylamine and leelamine into the reaction system, and smoothly obtained the corresponding sulfamides products in moderate yields (Figure ). We then tentatively tried the ligation of sulfamoyl fluoride 7g with p-cresol and estrone, which can afford the desired sulfamate ester products 12 and 13 in excellent yields (Figure ). Meanwhile, the cross-coupling reaction of 5d with bromobenzene derivatives 14 furnished 15 in high efficiency (Figure ). Finally, we tried the ligation of Fludioxonil and Formononetin, and successfully obtained the product 17 (Figure , D).