Nitrate 9-nitroalkyl

Oxidadve cross-conphng reactions of alkylated derivatives of activated CH compounds, such as malonic esters, acetylacetone, cyanoacetates, and ceitain ketones, v/ithnitroalkanes promoted by silver nitrate or iodine lead to the formation of the nitroalkylated products. This is an alternative way of performing Spj l reactions using cr.-halo-nitroalkanes. 

Goumont et al. exploited this kind of reactivity for the nucleophilic substitution of the hydrogen atom in position 5 by carbon nuclophiles <20030BC2192> (Scheme 18). These authors reported that 6,8-dinitrotetrazolo[l,5- ]pyr-idine 11 easily reacts with potassium nitropropenide to yield an adduct similar to those obtained with alcohols 12. This adduct when oxidized by cerium ammonium nitrate yields the nitroalkyl-substituted aromatic compound 64. 

A mixture of silver nitrite and iodine reacts with alkenes to give jS-nitroalkyl iodides, and therefore, provides a convenient route to a-nitroalkenes. Treatment of alkenes with ammonium nitrate and trifluoroacetic anhydride in the presence of ammonium bromide, followed by... 

Manganese(III) can oxidize carbonyl compounds and nitroalkanes to carboxy-methyl and nitromethyl radicals [186]. With Mn(III) as mediator, a tandem reaction consisting of an intermolecular radical addition followed by an intramolecular electrophilic aromatic substitution can be accomplished [186, 187). Further Mn(III)-mediated anodic additions of 1,3-dicarbonyl and l-keto-3-nitroalkyl compounds to alkenes and alkynes are reported in [110, 111, 188). Sorbic acid precursors have been obtained in larger scale and high current efficiency by a Mn(III)-mediated oxidation of acetic acid acetic anhydride in the presence of butadiene [189]. Also the nitromethylation of benzene can be performed in 78% yield with Mn(III) as electrocatalyst [190]. A N03 radical, generated by oxidation of a nitrate anion, can induce the 1,4-addition of aldehydes to activated olefins. NOj abstracts a hydrogen from the aldehyde to form an acyl radical, which undergoes addition to the olefin to afford a 1,4-diketone in 34-58% yield [191]. 

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