Three‐Component Reactions of Tetranitromethane with Olefins.

Abstract

Three-Component Reactions of Tetranitromethane with Olefins. -The reaction of tetranitromethane with two different olefins provides access to dinitroisoxazolidine derivatives in moderate yields. Key feature of the reaction is the use of a tri-or tetra--substituted olefin with a nucleophilic C-C double bond in the first step, which is able to react with tetranitromethane (II) to give a nitronic ester that is a poor 1,3-dipolarophile for the cyclization step. Good results are achieved with bicyclobutylidene (I) and 1-substituted cycloalkenes while dimethylbutene (XV) is less suitable. A wide range of olefins including electron-rich or electron-poor olefins can be used in the second step for the cyclization. Mixtures of diastereomers are obtained in most cases due to hindered rotation around the nitrogen. -(AVERINA, E. B.; BUDYNINA, E. M.; IVANOVA, O. A.; GRISHIN, Y. K.; GERDOV, S. M.; KUZNETSOVA, T. S.; ZEFIROV, N. S.; Russ.

The correlation consistent composite approach (ccCA): An alternative to the Gaussian-n methods

“…Tetranitromethane ͑TNM͒ can be used as a reagent for photonitration, for example, in syntheses of high-energy materials 91 or the heterocyclization of alkenes. 92 Early infrared 93 and electron gas diffraction studies 94,95 showed the structure of TNM to possess S 4 point group symmetry. Theoretical studies on this molecule are scarce.…”

Application of a Thermal β-Elimination Reaction toN-Alkoxy-3,3-dinitro­isoxazolidines: Synthesis of 3-Nitroisoxazolines

“…12 This synthetic route is based on the three-component reaction of tetranitro-and halotrinitromethanes with two alkenes, which gives 3,3-dinitroisoxazolidines with electron-withdrawing, aromatic, and heterocyclic substituents in good to excellent yields. [12][13][14][15] Interestingly, the three-component reactions of iodotrinitromethane with two alkenes proceed to give iododinitroisoxazolidines, which spontaneously undergo thermal b-elimination at room temperature to form 3-nitroisoxazolines. 15 Therefore the nitroisoxazolines of a target structure can be obtained through this synthetic sequence including the formation of dinitroisoxazolidines followed by b-elimination of nitro and alkoxy groups.…”