Sulfoximine-Assisted Asymmetric C(sp2)–H Bond Functionalizations

Abstract Sulfoximines, the monoaza analogues of sulfones featuring a stereogenic sulfur atom, have emerged as highly versatile molecular frameworks due to their remarkable chemical stability, tunable electronic properties, and broad applications across pharmaceutical, agrochemical, and material science domains. The presence of an N(sp2) center imparts both nucleophilic and basic characteristics, enabling strong coordination with transition metals and thus expanding their utility in diverse catalytic transformations. Leveraging this distinctive coordination ability, transition metal-catalyzed C–H functionalization directed by sulfoximines has recently gained significant attention as a powerful tool for the synthesis of complex and value-added molecular architectures. This account aims to summarize key advancements in the field of stereoselective C–H activation involving sulfoximines, both as reactive substrates and as chiral directing groups. Special emphasis is placed on their ability to mediate asymmetric C–H functionalization processes, where the inherent sulfur-centered chirality can be effectively transferred to neighboring carbon centers, offering new opportunities for constructing enantioenriched frameworks with high precision and efficiency.