Three-component Reactions of Tetranitromethane with Olefins

Specificity of the Reaction of Tetranitromethane with Alkenes in Nitromethane

“…An analogous behavior was described previously for some olefins having bulky substituents [14]. In the reaction of tetranitromethane with sterically unhindered alkenes, [2 + 3]-cycloaddition of nitronate E to the substrate leads to isoxazolidine derivatives H [1][2][3][4][5][6][7][8].…”

“…Scheme 2 illustrates the reaction mechanism which was proposed on the basis of modern views on the mechanism of tetranitromethane reactions with olefins, including the results of our studies [8,11]. Presumably, tetranitromethane and olefin initially form chargetransfer complex (CTC).…”

“…We previously showed that methylidenecyclobutane and bicyclobutylidene react with tetranitromethane in such solvents as petroleum ether and methylene chloride to give isoxazolidine derivatives [5][6][7][8]. We also found that the use of nitromethane as solvent changes neither the reaction direction nor the yield of the corresponding isoxazolidines.…”

“…In continuation of our recent studies on reactions of tetranitromethane with olefins containing small rings [5][6][7][8], in the present work we made an attempt to examine solvent effect on these reactions. We previously showed that methylidenecyclobutane and bicyclobutylidene react with tetranitromethane in such solvents as petroleum ether and methylene chloride to give isoxazolidine derivatives [5][6][7][8].…”

Polynitromethanes - Unique Reagents in the Synthesis of Nitro-Substituted Heterocycles

“…13 This pathway proceeds via the intermediacy of charge-transfer complexes (CTC) and then nitrocarbocations. These intermediates can undergo both O-(step A) and C-alkylation (step C) or rearrange (steps D and E) depending on the degree of positive charge delocalization.…”