Base-Promoted Reactions of Organostibines with Alkynes and Organic Halides to Give Chalcogenated (Z)‑Olefins and Ethers

Herein, with air-stable chalcogenated stibines (Sb–ER) as organometallic chalcogenating reagents, we developed base-promoted (Z)-hydro­chalcogenation of alkynes with DMSO/DMSO-d6 as hydrogen/deuterium sources, giving chalcogenated (Z)-olefins in good yields and with excellent regioselectivity. These reagents, easily synthesized from halostibines with in situ generated [Zn­(ER)2] at room temperature within a few minutes, could be also used in the base-promoted C­(sp3)–S­(Se) cross-coupling with C­(sp3)–X and copper-catalyzed C­(sp2)–S­(Se) cross-coupling with C­(sp2)–X (X = F, CI, Br, I) under mild conditions. This protocol could also be simply extended to organobismuth complexes (Bi–ER) with good functional tolerance.