Desilylative Nitration of Alkyl- and Allylsilanes with Nitronium Salts

Article abstract of DOI:10.1021/jo00380a046

Desilylative nitration of methyl- and ethylsilanes with nitronium tetrafluoroborate in sulfolane solution gives nitromethane and nitroethane, respectively.Higher alkylsilanes are also nitrated, but the reactions are followed by HNO2 elimination.The method represents the first successful nitrodesilylations at saturated carbon.Allylsilanes react cleanaly with NO2BF4 in methylene chloride solution to give nitropropanes in good to excellent yield.These reactions, however, involve initial attack by NO2⁺ on the allylic ?-system followed by fluoride-induced trimethylsilyl elimination and not direct desilylative nitration at saturated carbon. 1-(Trimethylsilyl)but-2-ene gives exclusive secondary 3-nitrobut-1-ene and not the primary direct nitrodesilylation product 1-nitrobut-2-ene.