Thiolation of Terminal Alkynes with Thiuram Disulfide Reagents Using Water as the Hydrogen Source: Stereoselective Synthesis of ( Z )-Vinyl Sulfides.

A stereoselective and environmentally friendly thiolation of terminal alkynes was reported. Thiuram disulfide reagents (tetramethylthiuram disulfide and tetraethylthiuram disulfide) that reacted with alkynes in dimethyl sulfoxide (DMSO)/H 2 O could give ( Z )-vinyl sulfides in good yields (up to 88%). This protocol features broad substrate scope, good stereoselectivity, high atom economy, good yields, and is transition metal-free. Mechanistic studies revealed that water and DMSO served as hydrogen sources, which greatly highlighted the unique reactivity of this special reaction involving two H-atom donors.