Sulfur-Mediated Aminothiolation of Terminal Alkynes: Regioselective Synthesis of Z-Trisubstituted Vinyl Sulfides

The first sulfur-mediated aminothiolation of terminal alkynes through a one-pot procedure under mild conditions has been established. This method is practical, easy to manipulate, and exhibits a wide substrate range with good functional group tolerance, resulting in Z-selective trisubstituted vinyl sulfides in moderate to high yields. The synthetic utility of this protocol is further highlighted by its applicability in scale-up reactions and late-stage modification of target products and drug molecules, making it a valuable tool for drug discovery. A mechanistic rationale is further supported by control experiments and DFT calculations.