Sulfur (VI)-containing compounds such as sulfonamide and sulfonates have been well established as privileged structural motifs in numerous FDA-approved drugs, and the synthesis of these compounds had been explored thoroughly over the past decades. In contrast, sulfonimidamide and sulfonimidate ester, the bioisosteres of sulfonamide and sulfonate, have been long been neglected in drug discovery due to the lack of commercial availability and synthetic accessibility. Compared to their oxygenated analogous, these compounds possess unique structural and physiochemical properties, such as intrinsic stereogenic sulfur centers, multiple hydrogen-bond acceptor and donor functionalities, high stability and good aqueous solubility. Fortunately, sulfonimidamides, sulfonimidate esters and other sulfonimindoyl compounds have recently gained significant attention of medicinal chemists. 4 Some of these sulfonimidoyl derivatives have been successfully used as new drugs and pesticides. Giving the growing significance of sulfonimidamides and sulfonimidate esters in drug discovery, considerable efforts have been exerted to develope new method for the synthesis of these sulfur (VI)-containing compounds in recent years. In addition to the classical substitution reactions of sulfonimidoyl chlorides, 6 the transformation of sulfinyamine derivatives, 7 and other elegant reactions 8 provide different protocols for the synthesis of sulfonimidamides and sulfonimidate esters.