Dialkylstibylsodium compounds have been prepared by cleavage of trialkylstibines with sodium in liquid ammonia. Reactions of the latter with epoxides, N-benzoylethylenimine and β-propiolactone have afforded several new functionally substituted organostibines. The different reactivities towards such cleavage of different alkly groups bound to antimony opens a route to the synthesis of asymmetrically