Strain-Enabled S-Arylation and S-Alkenylation of Sulfinamides

Converting commercially available and affordable chiral sulfinamides to pharmaceutically important chiral sulfoximines via SIV-functionalization is synthetically appealing, however, remains little developed due to the competing N-functionalization pathway. To address this challenge, we disclose a strain-enabled stereospecific and chemoselective S-arylation and S-alkenylation of sulfinamides using arynes and cyclic alkynes. The origin of high SIV-selectivity is elucidated by density functional theory (DFT) calculations, which reveals the potential involvement of a novel concerted mechanism. This method affords unprecedented chemical diversity on groups attached to the nitrogen center (N-R) that is valuable for diversity-oriented drug discovery