<i>N</i> ‐(Acyldithio)Saccharin: Design, Synthesis and Applications in Catalytic Enantioselective Disulfuration/Amination of Alkenes
Abstract
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.
Article Details
Authors (7)
Yu‐Xuan Huo
State Key Laboratory of Synergistic Chem‐Bio Synthesis School of Chemistry and Chemical Engineering Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs Shanghai Jiao Tong University Shanghai 200240 P.R. China
Ren‐Fei Cao
State Key Laboratory of Synergistic Chem‐Bio Synthesis School of Chemistry and Chemical Engineering Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs Shanghai Jiao Tong University Shanghai 200240 P.R. China
Jie Huang
Department of Chemistry
Ze‐Long Li
State Key Laboratory of Synergistic Chem‐Bio Synthesis School of Chemistry and Chemical Engineering Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs Shanghai Jiao Tong University Shanghai 200240 P.R. China
Zheng‐Wei Wei
State Key Laboratory of Synergistic Chem‐Bio Synthesis School of Chemistry and Chemical Engineering Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs Shanghai Jiao Tong University Shanghai 200240 P.R. China
Deng Zhu
Zhi‐Min Chen
State Key Laboratory of Synergistic Chem‐Bio Synthesis School of Chemistry and Chemical Engineering Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs Shanghai Jiao Tong University Shanghai 200240 P.R. China