Copper-catalyzed thiolation of terminal aromatic alkynes to access alkynyl disulfides

[Display omitted] •A copper-catalyzed thiolation by disulfur transfer to access alkynyl disulfides was developed.•Alkynyl disulfides and alkynyl sulfides were afforded due to the steric hindrance of dithiolsulfonates.•Fully substituted triazoles and pyrene-gemcitabine conjugate were prepared by this new approach. A copper-catalyzed thiolation of terminal aromatic alkynes by disulfur transfer to access alkynyl disulfides was developed. Different types of products were afforded due to the steric hindrance of dithiolsulfonates. Some important compounds, such as fully substituted triazoles and pyrene-gemcitabine conjugate were prepared by this new approach.