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- d 6 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( sp 3 )-S(Se) cross-coupling with C( sp 3 )-X and copper-catalyzed C( sp 2 )-S(Se) cross-coupling with C( sp 2 )-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.