Counterattack Reagents: Thiosilanes in the Conversion of Nitro Compounds to Thiohydroxamic Acids and Thiohydroximates.

Abstract Various primary nitro compounds were reacted sequentially with KH and Me 3 SiSSiMe 3 in THF to give thiohydroxamic acids in 56–92% yields. By the same strategy, a thiohydroxamic acid was obtained in 50% yield by treatment of trans -β-nitrostyrene with i -PrSLi in THF and then with Me 3 SiSSiMe 3 . Reaction of primary nitro compounds with n -BuLi and then with MeSSiMe 3 or PhSSiMe 3 produced the corresponding thiohydroximates in 61–78% yields. Secondary nitro compounds were converted to oximes in 68–96% yields by reaction with KH and Me 3 SiSSiMe 3 or MeSSiMe 3 in THF or 1,4-dioxane. In these “one-flask” reactions, thiosilanes Me 3 SiSSiMe 3 , MeSSiMe 3 , and PhSSiMe 3 acted as “counterattack reagents”