COUNTERATTACK REAGENTS: THIOSILANES IN THE CONVERSION OF NITRO COMPOUNDS TO THIOHYDROXAMIC ACIDS AND THIOHYDROXIMATES

Article abstract of DOI:10.1016/S0040-4020(01)89057-8

Various primary nitro compounds were reacted sequentially with KH and Me3SiSSiMe3 in THF to give thiohydroxamic acids in 56-92 percent yields.By the same strategy, a thiohydroxamic acid was obtained in 50 percent yield by treatment of trans-β-nitrostyrene with i-PrSLi in THF and then with Me3SiSSiMe3.Reaction of primary nitro compounds with n-BuLi and then with MeSSiMe3 or PhSSiMe3 produced the corresponding thiohydroximates in 61-78 percent yields.Secondary nitro compounds were converted to oximes in 68-96 percent yields by reaction with KH and Me3SiSSiMe3 or MeSSiMe3 in THF or 1,4-dioxane.In these "one-flask" reactions, thiosilanes Me3SiSSiMe3, MeSSiMe3, and PhSSiMe3 acted as "counterattack reagents".