The first examples of facile hydrothiophosphorylation of organyl vinyl sulfoxides are described. Nucleophilic addition of P,S-ambident secondary phosphine sulfides 1 and 2 to organyl vinyl sulfoxides 3-6 with potassium hydroxide at room temperature proceeds chemo- and regioselectively to give the corresponding bis(2-organylethyl)[2-(organylsulfinyl)ethyl]phosphine sulfides 7a-e in high isolated yields.
hydrothiophosphorylations - vinyl sulfoxides - secondary phosphine sulfides - nucleophilic additions