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Pericyclic [4+2] and [3+2] Cycloaddition Reactions of Nitroarenes in Heterocyclic Synthesis

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Chemistry of Heterocyclic Compounds Aims and scope

A summary is given of our results and literature data on the use of nitroarenes in pericyclic [4+2] and [3+2] cycloaddition reactions to give heterocycles fused with the original aromatic carbocycle. Highly electrophilic bicyclic nitroarenes, which are considered superelectrophiles, are capable of undergoing the Diels–Alder reaction with nucleophilic alkenes as C=C–N(O)=O heterodienes to give dihydro-1,2-oxazine N-oxides. Dinitrobenzenes, 1,3,5-trinitrobenzene, and their substituted derivatives and analogs as well as nitrobenzenes and 1,3-dinitrobenzenes fused with electron-withdrawing azoles and pyridine are capable of undergoing 1,3-dipolar cycloaddition as dipolarophiles at the C=C(NO2) bond with N-alkylazomethine ylides serving as 1,3-dipoles to give N-alkylpyrrolidines, pyrrolines, or pyrroles fused to an aromatic ring, depending on the structure of the nitro compound substrates. A relationship was found between the reactivity of the nitroarenes in pericyclic [4+2] and [3+2] cycloaddition reactions and the electrophilicity of these substrates.

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  1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Ave., Moscow, 119991, Russia

    S. A. Shevelev & A. M. Starosotnikov

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  1. S. A. Shevelev
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Correspondence to S. A. Shevelev.

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Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 102-128, January, 2013.

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Shevelev, S.A., Starosotnikov, A.M. Pericyclic [4+2] and [3+2] Cycloaddition Reactions of Nitroarenes in Heterocyclic Synthesis. Chem Heterocycl Comp 49, 92–115 (2013). https://doi.org/10.1007/s10593-013-1233-1

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