Abstract
Here, we have developed a simple, room temperature method for the nitration of olefins by using inexpensive sodium nitrite as a source of nitro groups in the presence of trifluoroacetic acid (TFA) and potassium persulfate (K2S2O8) under an open atmosphere. Styrenes and mono-substituted olefins give stereo-selective corresponding E-nitroolefins under optimized conditions, however, 1,1-bisubstituted olefins give a mixture of E- and Z-nitroolefins. The optimized conditions work well with electron-donating, electron-withdrawing, un-substituted and heterocyclic styrenes and mono-substituted olefins and give corresponding nitroolefins with good to excellent yields.
Highlights
Nitroole ns are intriguing synthetic units and have been used for the generation of biological, pharmaceutical, materials, and agrochemical relevant molecules.1a–e these are used as starting materials for various C–C bond forming reactions[2,3,4] and have been utilized in the synthesis of diverse chemically interesting molecules, viz., oximes, hydroxylamines, nitroalkanes, aliphatic amines, and nitroso compounds.5a,b considerable efforts have been made in the synthesis of nitroole ns including the Henry reaction, which involves the base mediated condensation of an aldehyde or ketone with a nitroalkane.[6]
The other approach used for the synthesis of nitroole ns involved the nitration of ole ns using a mixture of HNO3 and conc. sulfuric acids, where the reaction efficiency is signi cantly hampered by the production of a large amount of acid waste as well as nitrogen oxide fumes.[7]
Nitro alkenes are synthesized by the decarboxylative nitration of a,bunsaturated carboxylic acids.8a,b,9 the direct incorporation of a nitro group on an ole n is considered as the preferred approach
Summary
Nitroole ns are intriguing synthetic units and have been used for the generation of biological, pharmaceutical, materials, and agrochemical relevant molecules.1a–e these are used as starting materials for various C–C bond forming reactions[2,3,4] and have been utilized in the synthesis of diverse chemically interesting molecules, viz., oximes, hydroxylamines, nitroalkanes, aliphatic amines, and nitroso compounds.5a,b considerable efforts have been made in the synthesis of nitroole ns including the Henry reaction, which involves the base mediated condensation of an aldehyde or ketone with a nitroalkane.[6]. A mild and room temperature method was developed for the nitration of alkenes in the combination of sodium nitrite (NaNO2) and potassium persulfate (K2S2O8) and tri uoracetic acid (TFA) which offered high stereoselectivity for styrenes and mono-substituted ole ns (Fig. 1, le side, upper half). First reaction was performed by reacting 1a (1.0 mmol) with NaNO2, K2S2O8 and TFA in DCM under open atmosphere, the formation of required product, (E)-(2-nitrovinyl)benzene 2a was observed with the yield of 34% (entry 1).
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