The β-(trifluoromethyl) vinyl sulfides on treatment with n-BuLi/TMEDA at− 78° C were readily lithiated at an α-position of the sulfanyl group, and the generated β-trifluoromethyl-α- sulfanylvinyl anions were reacted with a variety of electrophiles to give the corresponding β- trifluoromethyl-α-functionalized-vinyl sulfides 4aa–4aq in good to excellent yields. The reactivity of some products has been examined. The palladium-catalyzed cross-coupling ...