<i>N</i> ‐(Acyldithio)Saccharin: Design, Synthesis and Applications in Catalytic Enantioselective Disulfuration/Amination of Alkenes
Yu‐Xuan Huo, Ren‐Fei Cao, Jie Huang, Ze‐Long Li, Zhiwei Wei, Deng Zhu, Zhi‐Min Chen
Abstract
We have designed and successfully synthesized N-(acyldithio)saccharin, which is a highly electrophilic, bench-stable, and user-friendly disulfurating reagent. This reagent can undergo reactions with diverse N-, S-, and C-nucleophiles at room temperature. In most cases, no additional catalyst is required, and the desired disulfides were readily obtained in moderate to excellent yields. With this reagent, late-stage disulfuration of pharmaceuticals and biomolecules was readily accomplished. For the first time, catalytic enantioselective disulfuration/amination of unactivated alkenes was achieved using this reagent. A series of chiral disulfides were obtained with high enantioselectivities and yields. The chiral disulfide products can be readily further transformed into chiral sulfonyl fluoride, chiral thiol, and structurally diverse disulfide products. Furthermore, we have evaluated the electrophilic reactivity of a series of disulfurating reagents based on density functional theory calculations, verifying the high reactivity of N-(acyldithio)saccharin both experimentally and theoretically.